CN103145999A - Preparation method of nano lignin with controllable particle size - Google Patents

Preparation method of nano lignin with controllable particle size Download PDF

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CN103145999A
CN103145999A CN2013100995443A CN201310099544A CN103145999A CN 103145999 A CN103145999 A CN 103145999A CN 2013100995443 A CN2013100995443 A CN 2013100995443A CN 201310099544 A CN201310099544 A CN 201310099544A CN 103145999 A CN103145999 A CN 103145999A
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lignin
alkali lignin
particle size
preparation
nano
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刘志明
刘国超
王海英
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Northeast Forestry University
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Northeast Forestry University
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Abstract

一种粒径可控纳米木质素的制备方法,它涉及一种纳米木质素的制备方法。本发明的目的是要解决现有制备纳米木质素的方法存在制备技术要求较高,操作复杂,且制备的纳米木质素粒径不可控的问题。方法:一、碱木质素预处理;二、研磨处理;三、制备碱木质素悬浮液;四、制备纳米木质素溶胶;五、制粉,即得到纳米木质素。优点;一、粒径控制在10nm~70nm之间,平均粒径为约为30nm,粒径为约为26nm的粒子含量最多;二、工艺简单,易操作,无环境污染。本发明主要用于制备纳米木质素。

Figure 201310099544

The invention discloses a preparation method of nano lignin with controllable particle size, which relates to a preparation method of nano lignin. The purpose of the present invention is to solve the problems that existing methods for preparing nano-lignin have relatively high preparation technical requirements, complicated operation and uncontrollable particle size of prepared nano-lignin. Methods: 1. pretreatment of alkali lignin; 2. grinding treatment; 3. preparation of alkali lignin suspension; 4. preparation of nanometer lignin sol; Advantages; 1. The particle size is controlled between 10nm and 70nm, the average particle size is about 30nm, and the particle size is about 26nm. The particle content is the most; 2. The process is simple, easy to operate, and has no environmental pollution. The invention is mainly used for preparing nano lignin.

Figure 201310099544

Description

A kind of preparation method of particle diameter controllable nano xylogen
Technical field
The present invention relates to a kind of preparation method of nano wood quality.
Background technology
Xylogen is a kind of complicated phenol polymer that is formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol).Xylogen is that occurring in nature is only second to cellulosic second largest renewable resources, and alkali lignin is the main component of papermaking digesting waste liquor, and abundant as renewable resources output, low price has degradability.Xylogen is as the secondary metabolites in growth and development of plants, in the cell walls lignification, xylogen penetrates in cell walls, be filled in the cell walls framework, strengthened the hardness of cell walls, strengthen mechanical holding power or the ultimate compression strength of cell, promoted the formation of mechanical tissue, be conducive to consolidate and support the effects such as plant materials and water conduction.Due to the chemical property of xylogen, make the plant xylem have Surface hydrophobicity of cell as insolubility and complicated phenol polymer simultaneously.Woodenly usually have a extensive future in fields such as biochemical industries as dispersion agent, sorbent material etc.The characteristics such as the high-specific surface area of nano wood quality have a extensive future in fields such as tensio-active agent, support of the catalyst, photochemical catalysis.But existing nano wood quality is mainly to utilize the dissolving of dioxane equal solvent, and technology of preparing is had relatively high expectations, as adopting supercritical technology etc., and complicated operation, and the nano wood quality particle diameter for preparing is uncontrollable.
Summary of the invention
The objective of the invention is to solve the existing method that prepare the nano wood quality and exist technology of preparing to have relatively high expectations, complicated operation, and the uncontrollable problem of nano wood quality particle diameter for preparing, and a kind of preparation method of particle diameter controllable nano xylogen is provided.
A kind of preparation method of particle diameter controllable nano xylogen specifically completes: one, alkali lignin pre-treatment: utilize the alkali extraction and acid precipitation method that alkali lignin is processed, namely obtain refining alkali lignin according to the following steps; Two, milled processed: the refining alkali lignin that step 1 is obtained carries out milled processed, then crosses 80~120 mesh sieves, namely obtains particle diameter less than the alkali lignin of 0.2mm; Three, preparation alkali lignin suspension: particle diameter is put into deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 5min~15min, namely obtain alkali lignin suspension; Four, preparation nano wood quality colloidal sol: the alkali lignin suspension that step 3 is obtained is placed in high pressure homogenizer, is to circulate under 900bar~l000bar 2~3 times at pressure, namely obtains nano wood quality colloidal sol; Five, powder process: temperature for-18 ° of C~-the nano wood quality colloidal sol that step 4 obtained under 2O ° C carries out freezingly, freezing 24h~26h, and then be-45 ° of C~-55 ° C lyophilize 24h~26h in temperature namely obtains the nano wood quality; Particle diameter described in step 3 is (1g~3g): 100mL less than the volume ratio of the quality of the alkali lignin of 0.2mm and deionized water.
Advantage of the present invention: one, the present invention utilizes the nano wood quality of supersound process and high-pressure homogeneous processing preparation, and nano wood quality particle diameter is controlled between 10mm~70mn, and median size is for being about 30nm, and particle diameter is that to be about the particle content of 26nm maximum; Two, technique of the present invention is simple, and is easy to operate, do not adopt the dioxane equal solvent, avoids environmental pollution, and the nano wood quality of the present invention's preparation has a extensive future in field of functional materials such as photochemical catalysis.
Description of drawings
Fig. 1 is infrared spectrogram, and in Fig. 1, a is the infrared spectrogram of the nano wood quality of test one preparation, and in Fig. 1, b is the infrared spectrogram of the refining alkali lignin of test one simultaneous test step 1 preparation;
Fig. 2 is the histogram of particle size distribution of the nano wood quality of test one simultaneous test preparation;
Fig. 3 is the histogram of particle size distribution of the nano wood quality of test one preparation;
Fig. 4 is the transmission electron microscope figure of the nano wood quality of test one preparation.
Embodiment
Embodiment one: present embodiment is a kind of preparation method of particle diameter controllable nano xylogen, specifically completes according to the following steps: one, alkali lignin pre-treatment: utilize the alkali extraction and acid precipitation method that alkali lignin is processed, namely obtain refining alkali lignin; Two, milled processed: the refining alkali lignin that step 1 is obtained carries out milled processed, then crosses 80~120 mesh sieves, namely obtains particle diameter less than the alkali lignin of 0.2mm; Three, preparation alkali lignin suspension: particle diameter is put into deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 5min-15min, namely obtain alkali lignin suspension; Four, preparation nano wood quality colloidal sol: the alkali lignin suspension that step 3 is obtained is placed in high pressure homogenizer, is to circulate under 900bar~1000bar 2~3 times at pressure, namely obtains nano wood quality colloidal sol; Five, powder process: carry out freezingly in temperature for the nano wood quality colloidal sol that under-18 ° of C~-20 ° C, step 4 is obtained, freezing 24h~26h, and then be-45 ° of C~-55 ° C lyophilize 24h~26h in temperature namely obtains the nano wood quality; Particle diameter described in step 3 is (1g~3g): 100mL less than the volume ratio of the quality of the alkali lignin of 0.2mm and deionized water.
Present embodiment is utilized the nano wood quality of supersound process and high-pressure homogeneous processing preparation, and nano wood quality particle diameter is controlled between 10nm-70nm, and median size is for being about 30nm, and particle diameter is that to be about the particle content of 26nm maximum.
Present embodiment technique is simple, and is easy to operate, do not adopt the dioxane equal solvent, avoids environmental pollution, and the nano wood quality of present embodiment preparation has a extensive future in field of functional materials such as photochemical catalysis.
embodiment two: the difference of present embodiment and embodiment one is: the alkali extraction and acid precipitation method specific operation process described in step 1 is as follows: at first alkali lignin is dissolved in the NaOH solution that concentration is 0.5mol/L-1.5mol/L, then carry out centrifugation, obtain supernatant liquor, to adopt massfraction under the water bath with thermostatic control of 55 ° of C~65 ° C of temperature be 12% aqueous hydrochloric acid transfers to the pH value of supernatant liquor till 6~7, and then carry out centrifugation, obtain the brown precipitation, adopt deionized water wash brown precipitation, wash be neutrality to the pH value of filtrate till, then be under 40 ° of C-50 ° of C, the precipitation after washing to be carried out drying in temperature, dry 20h~28h, namely obtain refining alkali lignin, the quality of described alkali lignin and concentration are that the volume ratio of the NaOH solution of 0.5mol/L~1.5mol/L is 1g:(5lnL-7lnL).Other are identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or two difference are: the refining alkali lignin that in step 2, step 1 is obtained carries out crossing 100 mesh sieves after milled processed.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the supersound process specific operation process described in step 3 is as follows: in ultrasonic frequency during to be the particle diameter that step 2 obtained under auxiliary of the ultrasonic wave of 40Hz~50Hz be scattered in deionized water less than the alkali lignin of 0.2mm.Other are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: circulate 2 times under 1000bar in step 4.Other are identical with embodiment one to four.
Adopt following verification experimental verification effect of the present invention
Test one: a kind of preparation method of particle diameter controllable nano xylogen, specifically complete: one, alkali lignin pre-treatment: utilize the alkali extraction and acid precipitation method that alkali lignin is processed, namely obtain refining alkali lignin according to the following steps; Two, milled processed: the refining alkali lignin that step 1 is obtained carries out milled processed, then crosses 80 mesh sieves, namely obtains particle diameter less than the alkali lignin of 0.2mm; Three, preparation alkali lignin suspension: the 10g particle diameter is put into the 500mL deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 5min, namely obtain alkali lignin suspension; Four, preparation nano wood quality colloidal sol: the alkali lignin suspension that step 3 is obtained is placed in high pressure homogenizer, is to circulate under 1000bar 2~3 times at pressure, namely obtains nano wood quality colloidal sol; Five, powder process: carry out freezingly in temperature for the nano wood quality colloidal sol that under-18 ° of C, step 4 is obtained, freezing 24h, and then be-50 ° of C lyophilize 24h in temperature namely obtains the nano wood quality.
Alkali lignin described in this testing sequence one is the industrial soda xylogen.
Alkali extraction and acid precipitation method specific operation process described in this testing sequence one is as follows: hundred first are dissolved in the 30g alkali lignin in the NaOH solution that 180mL concentration is 1.0mol/L, so carry out centrifugation, obtain supernatant liquor, to adopt massfraction under the water bath with thermostatic control of 60 ° of C of temperature be 12% aqueous hydrochloric acid transfers to the pH value of supernatant liquor till 6~7, obtain the brown precipitation, adopt deionized water wash brown precipitation, wash be neutrality to the pH value of filtrate till, then be under 45 ° of C, the precipitation after washing to be carried out drying in temperature, dry 24h namely obtains refining alkali lignin.
Under supersound process specific operation process described in this testing sequence three adds: in ultrasonic frequency during to be the particle diameter that step 2 obtained under auxiliary of the ultrasonic wave of 45Hz be scattered in deionized water less than the alkali lignin of 0.2mm.
Test a simultaneous test: a kind of preparation method of nano wood quality, specifically complete: one, alkali lignin pre-treatment: utilize the alkali extraction and acid precipitation method that alkali lignin is processed, namely obtain refining alkali lignin according to the following steps; Two, milled processed: the refining alkali lignin that step 1 is obtained carries out milled processed, then crosses 80 mesh sieves, namely obtains particle diameter less than the alkali lignin of 0.2mm; Three, preparation alkali lignin suspension: the 10g particle diameter is put into the 500mL deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 5min, namely obtain alkali lignin suspension; Four, powder process: carry out freezingly in temperature for the alkali lignin suspension that under-18 ° of C, step 3 is obtained, freezing 24h, and then be-50 ° of C lyophilize 24h in temperature namely obtains the nano wood quality.
Alkali lignin described in this testing sequence one is the industrial soda xylogen.
Alkali extraction and acid precipitation method specific operation process described in this testing sequence one is as follows: hundred first are dissolved in the 30g alkali lignin in the NaOH solution that 180mL concentration is 1.0mol/L, so carry out centrifugation, obtain Pu liquid, to adopt massfraction under the water bath with thermostatic control of 60 ° of C of temperature be 12% aqueous hydrochloric acid transfers to the pH value of supernatant liquor till 6~7, obtain the brown precipitation, adopt deionized water wash brown precipitation, wash be neutrality to the pH value of filtrate till, then be under 45 ° of C, the precipitation after washing to be carried out drying in temperature, dry 24h namely obtains refining alkali lignin.
Adopt Fourier transform infrared spectrometer to detect and test the refining alkali lignin of step 1 in a nano wood quality for preparing and test one simultaneous test, detected result as shown in Figure 1, Fig. 1 is infrared spectrogram, in Fig. 1, a is the infrared spectrogram of the nano wood quality of test one preparation, and in Fig. 1, b is the infrared spectrogram of the refining alkali lignin of step 1 in test one; As can be seen from Figure 1, the position of both main absorption peaks is consistent, and the intensity at peak is slightly had any different, and illustrates that homogenizing process is a physical process, does not relate to chemical reaction.Main absorption peak ownership in Fig. 1 is respectively: 1032.56cm -1The place is methylol (CH 2OH) absorption peak of C-O in, 1118.02cm -1The place is the stretching vibration absorption peak of ehter bond-O-, 1606.23cm -1, 1462.54cm -1The place is the vibration absorption peak of xylogen aromatic ring frame, 2937.68cm -1Be the stretching vibration absorption peak of methylene radical C-H, 3427.2lcm -1It is hydroxyl O-H stretching vibration absorption peak, result shown in Figure 1 shows that the nano wood quality of test one preparation contains abundant oxygen-containing functional group, homogenizing process is a physical process, therefore do not relate to chemical reaction, testing step 1 in the nano wood quality of a preparation and test one simultaneous test, to make with extra care the infrared analysis functional group of alkali lignin be consistent.
Adopt particle-size analyzer to detect the nano wood quality of test one simultaneous test preparation and the nano wood quality of test one preparation, detected result as shown in Figures 2 and 3; Fig. 2 is the histogram of particle size distribution of the nano wood quality of test one simultaneous test preparation; Fig. 3 is the histogram of particle size distribution of the nano wood quality of test one preparation; The nano wood quality particle diameter of testing as shown in Figure 3 a preparation is controlled between 10nm~60nm, and the nano wood quality median size of test one preparation is 31.3nm, and wherein particle diameter is that the particle content of 26.5nm is maximum; Test as shown in Figure 3 one and utilize the nano wood quality size distribution of supersound process and high-pressure homogeneous processing preparation more even, particle diameter distribution width is narrower.
Adopt the nano wood quality of transmission electron microscope observation test one preparation, observations as shown in Figure 4, Fig. 4 is the transmission electron microscope figure of the nano wood quality of test one preparation; Testing as shown in Figure 4 one utilizes the nano wood quality size distribution of supersound process and high-pressure homogeneous processing preparation more even.
Test two: this test with the difference of test one is: the refining alkali lignin that in step 2, step 1 is obtained carries out crossing 100 mesh sieves after milled processed.Other are identical with test one.
Test three: this test with the difference of test one is: the refining alkali lignin that in step 2, step 1 is obtained carries out crossing 120 mesh sieves after milled processed.Other are identical with test one.
Test four: this test with the difference of test one is: in step 3, the 12.5g particle diameter is put into the 500mL deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 5min, namely obtain alkali lignin suspension.Other are identical with test one.
Test five: this test with the difference of test one is: in step 3, the 15g particle diameter is put into the 500mL deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 5min, namely obtain alkali lignin suspension.Other are identical with test one.
Test six: this test with the difference of test one is: in step 3, the 10g particle diameter is put into the 500mL deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 10min, namely obtain alkali lignin suspension.Other are identical with test one.
Test seven: this test with the difference of test one is: in step 3, the 10g particle diameter is put into the 500mL deionized water less than the alkali lignin of 0.2mm, then carry out supersound process 15min, namely obtain alkali lignin suspension.Other are identical with test one.
Adopt particle-size analyzer to detect test one to the nano wood quality of test seven preparations, and calculate particle diameter mean value and the maximum particle diameter of content, as shown in table 1; The nano wood quality particle diameter of the present invention preparation is controlled as can be known by table 1.
Table 1
? Median size/nm Particle diameter/nm that content is maximum
Test one 31.3 26.5
Test two 30.7 25.4
Test three 30.5 25.4
Test four 32.6 27.2
Test five 35.2 28.3
Test six 30.9 25.4
Test seven 30.4 25.3

Claims (5)

1.一种粒径可控纳米木质素的制备方法,其特征在于粒径可控纳米木质素的制备方法是按以下步骤完成的:一、碱木质素预处理:利用碱溶酸沉法对碱木质素进行处理,即得到精制碱木质素;二、研磨处理:对步骤一得到的精制碱木质素进行研磨处理,然后过80-120目筛,即得到粒径小于0.2mm的碱木质素;三、制备碱木质素悬浮液:将粒径小于0.2mm的碱木质素放入去离子水中,然后进行超声处理5min~15min,即得到碱木质素悬浮液;四、制备纳米木质素溶胶:将步骤三得到的碱木质素悬浮液置于高压均质机中,在压强为900bar~1000bar下循环2~3次,即得到纳米木质素溶胶;五、制粉:在温度为-18°C~-20°C下对步骤四得到的纳米木质素溶胶进行冷冻,冷冻24h~26h,然后再在温度为-45°C~-55°C冷冻干燥24h~26h,即得到纳米木质素;步骤三中所述的粒径小于0.2mm的碱木质素的质量与去离子水的体积比为(1g~3g)∶100mL。1. a preparation method of particle size controllable nanometer lignin is characterized in that the preparation method of particle size controllable nanometer lignin is completed according to the following steps: one, alkali lignin pretreatment: utilize alkali-dissolving acid precipitation method to The alkali lignin is processed to obtain refined alkali lignin; 2. Grinding treatment: the refined alkali lignin obtained in step 1 is ground, and then passed through a 80-120 mesh sieve to obtain alkali lignin with a particle size less than 0.2mm Three, prepare alkali lignin suspension: put the alkali lignin whose particle size is less than 0.2mm into deionized water, then carry out ultrasonic treatment for 5min~15min to obtain alkali lignin suspension; four, prepare nano lignin sol: The alkali lignin suspension obtained in step 3 is placed in a high-pressure homogenizer, and circulated 2 to 3 times at a pressure of 900bar to 1000bar to obtain nano-lignin sol; 5. Milling: at a temperature of -18°C The nano-lignin sol obtained in step 4 is frozen at ~-20°C, frozen for 24h-26h, and then freeze-dried at a temperature of -45°C--55°C for 24h-26h to obtain nano-lignin; step The volume ratio of the mass of the alkali lignin with a particle size of less than 0.2mm to the volume ratio of deionized water described in the third is (1g-3g): 100mL. 2.根据权利要求1所述的一种粒径可控纳米木质素的制备方法,其特征在于步骤一中所述的碱溶酸沉法具体操作过程如下:首先将碱木质素溶于浓度为0.5mol/L~1.5mol/L的NaOH溶液中,然后进行离心分离,得到上清液,在温度55°C~65°C的恒温水浴下采用质量分数为12%的盐酸水溶液将上清液的pH值调至6~7为止,然后再次进行离心分离,得到褐色沉淀,采用去离子水洗涤褐色沉淀,洗涤至滤液的pH值呈中性为止,然后在温度为40°C~5O°C下对洗涤后的沉淀进行干燥,干燥20h~28h,即得到精制碱木质素;所述的碱木质素的质量与浓度为0.5mol/L~1.5mol/L的NaOH溶液的体积比为1g∶(5mL~7mL)。2. the preparation method of a kind of particle size controllable nanometer lignin according to claim 1, it is characterized in that the concrete operation process of the alkali-dissolving acid precipitation method described in step 1 is as follows: first the alkali lignin is dissolved in the concentration of 0.5mol/L~1.5mol/L NaOH solution, and then centrifuged to obtain the supernatant, and the supernatant was distilled with a 12% hydrochloric acid aqueous solution in a constant temperature water bath at a temperature of 55°C~65°C. The pH value of the filtrate was adjusted to 6-7, and then centrifuged again to obtain a brown precipitate. The brown precipitate was washed with deionized water until the pH value of the filtrate was neutral, and then at a temperature of 40°C to 50°C Next, the precipitate after washing is dried and dried for 20h to 28h to obtain refined alkali lignin; the volume ratio of the quality of the alkali lignin to the NaOH solution whose concentration is 0.5mol/L to 1.5mol/L is 1g: (5mL ~ 7mL). 3.根据权利要求1或2所述的一种粒径可控纳米木质素的制备方法,其特征在于步骤二中对步骤一得到的精制碱木质素进行研磨处理后过100目筛。3. A method for preparing nano-lignin with controllable particle size according to claim 1 or 2, characterized in that in step 2, the refined alkali lignin obtained in step 1 is ground and passed through a 100-mesh sieve. 4.根据权利要求1或2所述的一种粒径可控纳米木质素的制备方法,其特征在于步骤三中所述的超声处理具体操作过程如下:在超声频率为40Hz~50Hz的超声波辅助下将步骤二得到的粒径小于0.2mm的碱木质素分散于去离子水中。4. according to the preparation method of a kind of particle size controllable nano-lignin described in claim 1 or 2, it is characterized in that the specific operation process of ultrasonic treatment described in step 3 is as follows: be 40Hz~50Hz ultrasonic assisted at ultrasonic frequency Next, disperse the alkali lignin with a particle size less than 0.2mm obtained in step 2 in deionized water. 5.根据权利要求1或2所述的一种粒径可控纳米木质素的制备方法,其特征在于步骤四中在1000bar下循环2次。5. A method for preparing nano-lignin with controllable particle size according to claim 1 or 2, characterized in that in step 4, the process is performed twice at 1000 bar.
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