CN112899325A - Purification of alkali-ozone combined black liquor from lignocellulose pretreated by XAD 16N macroporous adsorption resin and its cyclic utilization - Google Patents
Purification of alkali-ozone combined black liquor from lignocellulose pretreated by XAD 16N macroporous adsorption resin and its cyclic utilization Download PDFInfo
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Abstract
本发明公开了一种XAD 16N大孔吸附树脂净化碱黑液及利用该净化废液在碱结合臭氧预处理木质纤维素过程中实现循环利用。该方法将碱处理木质纤维素后获得的处理黑液经过XAD 16N大孔吸附树脂吸附其中的木质素及其降解产物，可以在净化碱黑液的同时，节约下一轮碱的用量。XAD 16N大孔吸附树脂吸附碱黑液后通过无水乙醇浸泡和NaOH溶液淋洗后可实现循环使用；乙醇经蒸馏可实现重复使用；用于淋洗的NaOH溶液在补足浓度后可用于木质纤维素的处理。该净化方法能够实现碱黑液、洗涤液、吸附剂、乙醇、淋洗碱液的循环使用，达到节约水资源和减少污染的目的。同时，处理过程较为简单，处理条件温和，净化碱黑液处理木质纤维素对木质纤维素的酶解率影响小。The invention discloses an XAD 16N macroporous adsorption resin for purifying alkali black liquor and utilizing the purified waste liquor to realize recycling in the process of alkali-combined ozone pretreatment of lignocellulose. In the method, the treated black liquor obtained after alkali treatment of lignocellulose is subjected to XAD 16N macroporous adsorption resin to adsorb the lignin and its degradation products, which can purify the alkali black liquor and save the consumption of the next round of alkali. XAD 16N macroporous adsorption resin adsorbs alkali black liquor and can be recycled after soaking in absolute ethanol and leaching with NaOH solution; ethanol can be reused after distillation; NaOH solution used for leaching can be used for wood fiber after supplementing the concentration element processing. The purification method can realize the recycling of alkali black liquor, washing liquid, adsorbent, ethanol and leaching alkali liquor, so as to achieve the purpose of saving water resources and reducing pollution. At the same time, the treatment process is relatively simple, the treatment conditions are mild, and the treatment of lignocellulose with purified alkali black liquor has little effect on the enzymatic hydrolysis rate of lignocellulose.
Description
Technical Field
The invention belongs to the field of biomass energy, and particularly relates to a black liquor for purifying alkali and pretreating lignocellulose by combining ozone through XAD 16N macroporous adsorption resin and a recycling method thereof.
Background
Cellulose and hemicellulose are possible sources of fermentable sugars, but lignin, which provides further strength to the plant cell wall, hinders enzymatic hydrolysis of cellulose. The cellulose enzymolysis rate in the biomass can only reach about 13.3 percent without any pretreatment, and the cellulose enzymolysis rate can be improved to more than 90 percent after proper pretreatment. The effectiveness of the pretreatment depends on the physical structure, chemical composition and processing conditions of the raw materials.
At present, the lignocellulose raw material pretreatment method comprises a physical method, a physicochemical method, a chemical method, a biological method and a combined pretreatment method. The alkaline pretreatment has the functions of removing lignin and improving the utilization rate of the lignocellulose biomass raw material, in order to improve the sugar yield of the biomass raw material, the alkaline pretreatment condition is generally treated for 1 to 3 hours at 85 to 135 ℃ or for 1 day or longer at 50 to 65 ℃, but the effects of removing the lignin and improving the cellulose hydrolysis by single alkaline treatment are not ideal; ozone (O)3) Can effectively degrade lignin and a small amount of hemicellulose in the straws, and the early-stage research of the project discovers that alkali is combined with O3Pretreatment (NaOH-O)3Pretreatment) the lignin removal rate in the corn straw process reaches 84.35%, the cellulose enzymolysis rate reaches 91.73%, and the hemicellulose enzymolysis rate reaches 36.59%. However, in the alkaline treatment process, a large amount of high-alkali waste water is produced, and the color of lignocellulose pretreated with an alkaline solution is usually dark black, and is therefore also referred to as black liquor. The black liquor mainly contains phenolic substances generated after lignin degradation, micromolecular lignin dissolved by alkali, a small amount of glycan, a trace amount of xylose, a trace amount of glucose, residual NaOH and the like, and if the black liquor is directly discharged into a water body, the alkaline black liquor containing a large amount of fibers, pigments and inorganic saltsThe water body can be blackened, dissolved oxygen in water can be greatly consumed by high-concentration organic pollutants, water quality is influenced, the pH value of the water body can be sharply increased by alkaline substances in the alkali black liquor, the balance of the water body environment is damaged, the cost can be increased by adopting industrial purification, resources are saved to the maximum extent, the cost is reduced, the environment is protected, and the alkali black liquor is designed to be recycled. However, the alkaline black liquor contains inhibiting products such as aromatic compounds, which affects the recycling of the alkaline black liquor. Therefore, the development of a method for recycling the alkaline black liquor has important practical significance. This patent adopts XAD 16N macroporous absorbent resin purification treatment to obtain purifying black liquid, makes it can get into next round alkali and combines ozone pretreatment lignocellulose process, practices thrift the quantity of alkali, reduces living beings preliminary treatment cost.
Disclosure of Invention
The invention aims to provide a process for purifying alkali black liquor by XAD 16N macroporous adsorption resin to realize alkali-ozone combined pretreatment of lignocellulose high-efficiency circulation, and the enzymolysis effect of the alkali waste liquor after adsorption is not influenced when the alkali waste liquor is subjected to next round of lignocellulose treatment.
The invention provides a black liquor for purifying alkali and combining ozone to pretreat lignocellulose by using XAD 16N macroporous adsorption resin and a recycling method thereof, which comprises the following steps:
(1) treating lignocellulose with alkali liquor, filtering the lignocellulose, draining, and respectively collecting the treated lignocellulose and alkali black liquor; washing the treated lignocellulose with water until the pH value is 8-10, and collecting washing black liquor containing alkali liquor; controlling the water content to be 5-15 times of the dry weight of the lignocellulose, then introducing ozone with a certain concentration, treating for a period of time, and performing enzymolysis on the ozone waste liquid and the lignocellulose after the treatment to obtain hydrolysate rich in glucose and xylose for further biomass energy utilization;
(2) absorbing the alkali black liquor and the washing black liquor by XAD 16N macroporous absorption resin to obtain purified black liquor, and adjusting the alkali concentration of the obtained purified black liquor and then carrying out a new round of alkali treatment on lignocellulose (repeating the step (1));
(3) the adsorbed XAD 16N macroporous adsorption resin can be reused after regeneration.
In the step (1), the raw material of lignocellulose comprises: corn stover, wood chips, rice straw, and wheat straw;
the lignocellulose is crushed to 40-80 meshes before alkali treatment;
the alkali liquor can be sodium hydroxide or potassium hydroxide solution with the mass fraction of 0.5% -4%;
the mass ratio of the lignocellulose to the alkali liquor is 1: 10-30;
the conditions of the alkali treatment are as follows: treating at 40-100 deg.C for 1-4 hr.
In the step (1), the ozone is introduced at a concentration of 50-100mg/L and the ozone action time is 10-60 min.
In the step (1), the ozone waste liquid and the lignocellulose are subjected to enzymolysis by methods disclosed in the prior art, such as adding xylanase and cellulase for hydrolysis.
In the above method step (2), the method of the adsorption treatment includes the following method 1) or 2):
1) mixing the alkali black liquor, the washing black liquor and XAD 16N macroporous adsorption resin according to the mass ratio of 3-8: 1 (specifically 3:1, 4:1, 8:1), balancing in a 120-jar 180r/mim shaking table at 24-32 ℃ for 1.5-4h, and filtering to obtain purified black liquor;
2) and (3) passing the alkali black liquor and the washing black liquor through an XAD 16N macroporous adsorption resin column, wherein the column chromatography adsorption capacity is 3-8 column volume amounts, and collecting effluent liquid to obtain purified black liquor.
In the step (2), the alkali black liquor and the washing black liquor can be mixed according to the mass ratio of 1: 5-9, and then carrying out adsorption treatment.
The purified black liquor obtained by the method is added with alkali to be adjusted to proper concentration, and can be used as alkali liquor for a new round of alkali treatment process of lignocellulose; the enzymolysis rate of lignocellulose treated by purifying black liquor has little difference with the enzymolysis rate of cellulose treated by combining the initial alkali and the ozone.
The specific method for circularly applying the purified black liquor comprises the following steps: according to the amount of the treated lignocellulose, the ratio of 1 part by mass of lignocellulose: 10-30 parts by mass of sodium hydroxide or potassium hydroxide with the concentration of 0.5-4%, mixing the adsorption alkali black liquor and the adsorption washing black liquor according to the proportion to obtain total adsorption black liquor, adding sodium hydroxide or potassium hydroxide into the total adsorption black liquor to enable the alkali content to reach 0.5-4%, and then entering the next round of lignocellulose treatment.
The XAD 16N macroporous adsorption resin adsorbing the alkali black liquor can also be regenerated and then used continuously.
The specific regeneration method is as follows: soaking the adsorbed XAD 16N macroporous adsorption resin in 2-6 times of anhydrous ethanol, replacing the anhydrous ethanol every 3-6h, leaching for 2-4 times by using NaOH solution with the mass fraction of 1-5% and 2-6 times of the volume of the XAD 16N macroporous adsorption resin, washing to be neutral by using deionized water, draining, and storing; and combining the absolute ethyl alcohol washing solutions, concentrating in vacuum, collecting ethyl alcohol for regeneration of macroporous adsorption resin in the next round, drying and further utilizing the residual pasty substances which are mainly lignin degradation products, and adsorbing by washing alkali liquor to be used for treating lignocellulose.
The XAD 16N macroporous adsorption resin provided by the invention can purify alkaline black liquor to realize an alkaline-ozone-combined pretreatment lignocellulose efficient circulation process, and the adsorbed alkaline waste liquor has little influence on the cellulose enzymolysis effect when being subjected to next round of lignocellulose treatment.
The method for realizing the recycling of the purified waste liquid in the process of pretreating the lignocellulose by combining alkali with ozone also belongs to the protection scope of the invention.
Adding XAD 16N macroporous adsorption resin into alkali black liquor generated by treating lignocellulose with alkali and ozone and washing black liquor generated in the lignocellulose washing process for adsorption, removing inhibition products in the black liquor, adding sodium hydroxide or potassium hydroxide to the original concentration and supplementing the volume of the black liquor, and using the mixture for treating next batch of lignocellulose; the XAD 16N macroporous adsorption resin is subjected to ethanol treatment, ethanol is distilled, and the alkaline liquor used for leaching can be reused, so that the recycling of black liquor, washing liquid, adsorbent, ethanol and leaching alkaline liquor is realized under the condition of ensuring the lignocellulose enzymolysis rate, the wastewater discharge is reduced, and the purposes of saving resources, reducing cost and protecting environment are achieved.
Drawings
FIG. 1 is a graph of lignin removal rate for different sorbent adsorption cycle black liquor under the conditions of example 1, wherein (a) the effect of XAD 16N sorbent adsorption cycle black liquor on lignin removal rate; (b) the effect of the XAD 4 adsorbent on lignin removal rate by adsorption of the circulating black liquor.
FIG. 2 shows the number of cycles and the degree of hydrolysis of black liquor-treated straw after adsorption under the conditions of example 1.
FIG. 3 is a scanning electron micrograph of XAD 16N adsorbent treated with the method of example 1 under the conditions of example 1, after 3 cycles of alkaline black liquor treatment, fresh corn stover (A) and untreated straw (B) in combination with ozone.
Detailed Description
The present invention is described below with reference to specific embodiments, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set up and the results averaged.
Example 1
Mixing lignocellulose (corn straw, crushed to 60 meshes) and 2% sodium hydroxide or potassium hydroxide solution (dry weight basis) according to the mass ratio of 1:15, processing at 80 ℃ for 2h, filtering and squeezing the lignocellulose, and separating to obtain alkali black liquor; washing the lignocellulose obtained by filtering with tap water or purified water to pH9, filtering, and collecting residue and filtrate (washing black liquor); controlling the mass of filter residue to be 7.5 times of that of the initial lignocellulose, and introducing ozone, wherein the ozone concentration is 78mg/L, and the ozone action time is 25 min; adding acid to adjust the pH value to 5.0, adding xylanase and cellulase to carry out hydrolysis under the conventional control condition, and obtaining hydrolysate rich in glucose and xylose for further biomass energy utilization.
Mixing alkali black liquor and washing black liquor according to the mass ratio of 1: 7 and mixing the mixed solution with XAD 16N macroporous adsorption resin according to the mass ratio of 4:1, mixing, balancing in a shaking table at 28 ℃ and 150r/min for 2.5h, and filtering to obtain purified black liquor; or loading the processed XAD 16N macroporous adsorption resin into a column, directly carrying out column adsorption on the alkali black liquor, wherein the adsorption capacity of the column chromatography is 4 column volume amounts, and flowing out to obtain purified black liquor.
The recycling application method of the alkali black liquor comprises the following steps: and adding sodium hydroxide or potassium hydroxide into the adsorbed purified black liquor to ensure that the alkali mass fraction reaches 2 percent, and then carrying out next round of lignocellulose treatment.
When the unadsorbed alkali black liquor after 3 times of circulation is reused for treating lignocellulose, the cellulose hydrolysis rate is 76.27%, and the straw enzymolysis rate obtained by treating lignocellulose after the alkali black liquor after 3 times of circulation is absorbed by XAD 16N macroporous absorption resin is increased to 86.89%. The cellulose hydrolysis rate of fresh alkali liquor which adopts alkali and ozone to treat the straws is 87.66 percent.
The regenerating method of XAD 16N macroporous adsorption resin comprises the following steps: the usage amount of the absolute ethyl alcohol is 3 times of the volume of the XAD 16N macroporous adsorption resin, the absolute ethyl alcohol is changed every 4 hours, the absolute ethyl alcohol is soaked until the absolute ethyl alcohol is colorless, the absolute ethyl alcohol is leached for 3 times by using a NaOH solution with the mass fraction of 4 percent and the volume of 3 times of the volume of the macroporous adsorption resin, the absolute ethyl alcohol is washed to be neutral by using deionized water, and the absolute ethyl alcohol is stored after the water is drained. And combining the absolute ethyl alcohol washing solutions, concentrating in vacuum, collecting ethyl alcohol, using the collected ethyl alcohol for next round of macroporous adsorption resin, drying the rest paste-like substances which are mainly lignin degradation products and can be further used, and using the washing alkali liquor for adsorption and treatment of lignocellulose.
Example 2
Mixing lignocellulose (corn straw, crushed to 40 meshes) and sodium hydroxide or potassium hydroxide solution with the mass fraction of 4% (by dry weight) according to the mass ratio of 1:10, processing at 100 ℃ for 1h, filtering and squeezing the lignocellulose, and separating to obtain alkali black liquor; washing the lignocellulose obtained by filtering with tap water or purified water to pH 10, filtering, and collecting the filter residue and filtrate (washing black liquor); controlling the mass of filter residue to be 5 times of that of the initial lignocellulose, and introducing ozone, wherein the ozone concentration is 100mg/L, and the ozone action time is 10 min; adding acid to adjust the pH value to 5.0, adding xylanase and cellulase to carry out hydrolysis under the conventional control condition, and obtaining hydrolysate rich in glucose and xylose for further biomass energy utilization.
Mixing alkali black liquor and washing black liquor according to the mass ratio of 1: 5, mixing the mixed solution with XAD 16N macroporous adsorption resin according to the mass ratio of 3:1, mixing, balancing for 1.5h in a shaking table at 24 ℃ and 150r/min, and filtering to obtain purified black liquor; or the treated macroporous adsorption resin is loaded into a column, the alkali black liquor is directly subjected to column adsorption, the adsorption capacity of the column chromatography is 3 column volume amounts, and the purified black liquor flows out.
The recycling application method of the alkali black liquor comprises the following steps: adding sodium hydroxide or potassium hydroxide into the purified black liquor to make the alkali mass fraction reach 4 percent, and then performing next round of lignocellulose treatment;
when the unadsorbed alkali black liquor is recycled for 3 times and then used for treating lignocellulose, the cellulose hydrolysis rate is 73.40%, and the straw enzymolysis rate obtained by treating lignocellulose after the alkali black liquor after being recycled for 3 times is absorbed by XAD 16N macroporous absorption resin is increased to 84.37%. The cellulose enzymolysis rate of the fresh alkali liquor which adopts alkali and ozone to treat the straws is 85.43 percent.
The regenerating method of XAD 16N macroporous adsorption resin comprises the following steps: the usage amount of the absolute ethyl alcohol is 2 times of the volume of the macroporous adsorption resin, the absolute ethyl alcohol is replaced every 3 hours, the macroporous adsorption resin is soaked until the absolute ethyl alcohol is colorless, a NaOH solution with the mass fraction of 5 percent which is 2 times of the volume of the macroporous adsorption resin is used for leaching for 2 times, the macroporous adsorption resin is washed to be neutral by deionized water, and the macroporous adsorption resin is stored after water is drained. And combining the absolute ethyl alcohol washing solutions, concentrating in vacuum, collecting ethyl alcohol, using the collected ethyl alcohol for next round of macroporous adsorption resin, drying the rest paste-like substances which are mainly lignin degradation products and can be further used, and using the washing alkali liquor for adsorption and treatment of lignocellulose.
Example 3
Mixing lignocellulose (corn straw, crushed to 80 meshes) and 0.5% sodium hydroxide or potassium hydroxide solution (dry weight basis) according to the mass ratio of 1:30, processing at 40 ℃ for 4h, filtering and squeezing the lignocellulose, and separating to obtain alkali black liquor; washing the lignocellulose obtained by filtering with tap water or purified water to pH 8, filtering, and collecting the filter residue and filtrate (washing black liquor); controlling the mass of filter residue to be 15 times of that of the initial lignocellulose, and introducing ozone, wherein the ozone concentration is 50mg/L, and the ozone action time is 60 min; adding acid to adjust the pH value to 5.0, adding xylanase and cellulase to carry out hydrolysis under the conventional control condition, and obtaining hydrolysate rich in glucose and xylose for further biomass energy utilization.
Mixing alkali black liquor and washing black liquor according to the mass ratio of 1: 9 and mixing the mixed solution with XAD 16N macroporous adsorption resin according to the mass ratio of 8:1, mixing, balancing in a shaking table of 150r/min at the temperature of 32 ℃ for 4 hours, and filtering to obtain purified black liquor; or the treated macroporous adsorption resin is loaded into a column, the alkali black liquor is directly subjected to column adsorption, the adsorption capacity of the column chromatography is 8 column volume amounts, and the purified black liquor flows out.
The recycling application method of the alkali black liquor comprises the following steps: sodium hydroxide or potassium hydroxide is added into the purified black liquor to make the alkali mass fraction reach 0.5 percent, and then the next round of lignocellulose treatment can be carried out.
When the unadsorbed alkali black liquor is used for treating lignocellulose after being circulated for 3 times, the cellulose hydrolysis rate is 72.89%, and the straw enzymolysis rate of treating lignocellulose after the alkali black liquor after being circulated for 3 times is absorbed by XAD 16N macroporous absorption resin is increased to 81.35%. The cellulose enzymolysis rate of the fresh alkali liquor which adopts alkali and ozone to treat the straws is 84.25 percent.
The regenerating method of XAD 16N macroporous adsorption resin comprises the following steps: the usage amount of the absolute ethyl alcohol is 6 times of the volume of the XAD 16N macroporous adsorption resin, the absolute ethyl alcohol is changed every 6 hours, the absolute ethyl alcohol is soaked until the absolute ethyl alcohol is colorless, 1% NaOH solution 6 times of the volume of the macroporous adsorption resin is used for leaching for 4 times, the solution is washed to be neutral by deionized water, and the solution is stored after water is drained. And combining the absolute ethyl alcohol washing solutions, concentrating in vacuum, collecting ethyl alcohol, using the collected ethyl alcohol for next round of macroporous adsorption resin, drying and further utilizing the residual pasty substances which are mainly lignin degradation products, and using the washing alkali liquor for treating lignocellulose after adsorption.
The relevant test tests and results of the above examples are shown below:
1. influence of adsorption circulation black liquor of different adsorbents on lignin removal rate
Taking the mixture obtained in the example 1, performing the third circulation treatment, and then mixing the mixture according to the mass ratio of 1: 7, adding 3g of XAD 16N adsorbent into 20mL of mixed alkaline black liquor and washing black liquor, shaking uniformly, placing in a 150rpm shaking table at 28 ℃ for balancing for different time (1h, 1.5h, 2h, 2.5h, 3h, 3.5h and 4h), and measuring the lignin content in the alkaline black liquor after adsorption is finished, wherein the method comprises the following steps:
accurately weighing 20mL of alkali black liquor after adsorption treatment, adding 560mL of 3% sulfuric acid for hydrolysis, reacting for 1h in a high-pressure steam sterilization pot at 121 ℃, filtering by using a constant-weight sand core funnel, washing by using hot distilled water to be neutral, and then putting the sand core funnel into a 105 ℃ oven to reach constant weight, namely the content of acid-insoluble lignin. Filtering to obtain filtrate, and measuring ultraviolet absorption value at wavelength of 205nm to obtain content (B) of acid soluble lignin in the filtrate.
B＝A×D/110(g/1000mL)
A is light absorption value; d, dilution times of the filtrate; 110: extinction coefficient, L/(g × cm)
The effect of adsorption time on the adsorption effect of the alkaline black liquor is shown in fig. 1 (a). As can be seen from the graph, the lignin removal rate of the adsorbent showed an increasing trend as the adsorption time was increased, and the lignin removal rate of XAD 16N was 66.62% when the adsorption time was 2.5h, and then the lignin removal rate tended to be stable as the time was increased.
Adsorption effect of control adsorbent:
in the adsorption method, XAD 16N macroporous adsorption resin is replaced by XAD 4 macroporous adsorption resin, the rest steps and conditions are unchanged, and the adsorption effect is shown in figure 1 (b). When the adsorption time was 2.5h, the lignin removal was 49.74%, which was 16.88% lower than XAD 16N.
The experimental results show that: the XAD 4 macroporous adsorption resin also has the function of adsorbing lignin, but the removal rate of the lignin is far lower than that of the XAD 16N macroporous adsorption resin, which shows that macromolecular substances in the alkaline black liquor can be better removed by using the XAD 16N macroporous adsorption resin, and the recycling of the alkaline black liquor is realized.
2. Influence of the adsorbent on the enzymolysis rate of the alkali-ozone-combined pretreated corn straws after the alkali black liquor is adsorbed and purified
Treating the alkaline black liquor circulating for the 3 rd time by using XAD 16N adsorbent under the conditions of example 1, supplementing the alkaline black liquor to the original volume and concentration after adsorption (the specific numerical value is required to participate in the cyclic application method part of the alkaline black liquor in example 1), treating fresh corn straws by using the alkaline black liquor, washing straw residues to be neutral, and measuring the enzymolysis rate, wherein the measuring method comprises the following steps:
a corn stalk sample pretreated with sodium hydroxide and ozone (the specific treatment method is the same as that in example 1) is placed in a 100mL triangular flask, and 60mL of acetic acid-sodium acetate buffer solution (0.1mol/L pH 4.8) is added. Adding 120 mu L of cycloheximide and 160 mu L of tetracycline hydrochloride, adding 40 mu L of xylanase (45.8U/mL), oscillating in a water bath at 50 ℃ for enzymolysis for 24 hours (120r/min), cooling to room temperature after the enzymolysis reaction is finished, adding 120 mu L of cellulase (77.8U/mL) and 20 mu L of beta-glucosidase (690.4U/mL), oscillating at 50 ℃ for enzymolysis for 72 hours (120 r/min). Filtering with 200 mesh cell sieve after enzymolysis, recovering enzymolysis liquid, measuring glucose content, and calculating cellulose enzymolysis conversion rate.
The method for measuring the glucose content comprises the following steps: with reference to NREL/TP-510-42621, the assay conditions were as follows: the instrument comprises the following steps: agilent 1200; a chromatographic column: rezex ROA and corresponding guard columns; a detector: a difference detector; sample introduction amount: 20 mu L of the solution; mobile phase: 0.005M H2SO4Filtering with 0.22 μm filter membrane, and degassing; flow rate: 0.6 mL/min; column temperature: and 65 ℃.
C1-glucose concentration in the enzymatic hydrolysate, mg/mL;
v is the volume of the enzymolysis solution, mL;
0.90-coefficient of conversion of glucose to fiber;
m represents the mass of the corn stalks in mg;
W1percent cellulose content in straw。
The enzymolysis rate of the straw obtained by the post-treatment of the adsorbed alkali black liquor is shown in figure 2, which is different from the enzymolysis rate of the straw obtained by the post-treatment of the alkali black liquor for different times. As can be seen from the figure, compared with the straw enzymolysis rate of the 4 th time of recycling the alkaline black liquor, the straw enzymolysis rate obtained by the post-treatment of absorbing the alkaline black liquor by the XAD 16N adsorbent is remarkably improved, and is increased from 76.27% to 86.89%. The enzymolysis rate after adsorption treatment is larger than that of the 1 st time of cyclic utilization, the enzymolysis rate is only 0.77 percent lower than that of the non-cyclic utilization, and the enzymolysis rate is 10.62 percent higher than that of the 4 th cycle alkali black liquor.
3. Scanning electron microscope observation of purified alkali black liquor combined with ozone pretreated corn stalks
The concentration and volume of the alkali black liquor after the adsorption treatment by the adsorbent are supplemented to the initial state, fresh corn straws are treated according to the alkali and ozone pretreatment method in the embodiment 1, and after the reaction is finished, filtrate and the treated corn straws are respectively recovered through suction filtration. Washing the corn stalks with deionized water to be neutral, recovering the washed corn stalks, and drying the corn stalks in a 55 ℃ drying oven. And uniformly coating the sample on the conductive adhesive tape of the sample plate, spraying gold for 60s, detecting in a NeoScopeJCM-5000 scanning electron microscope, adopting high vacuum degree, and respectively amplifying to different times for observation. Scanning electron microscopy of sorbent treated alkaline black liquor combined with ozone treated corn stover and untreated straw is shown in figure 3. The alkaline black liquor used for treating the straws in figure 3(A) is subjected to XAD 16N macroporous adsorption resin adsorption treatment, and the structure torn on the surface of the straws can be seen to be stripped, the structure filled between celluloses is effectively removed, a thin layer of the structure is left, and a large number of holes and depressions are attached. Compared with the untreated straw in FIG. 3(B), the structure of the pretreated straw is effectively destroyed. The straw lignin obtained by alkali-combined ozone treatment of the alkali black liquor treated by XAD 16N has good removal effect, and the straws are fully swelled and split by the alkali liquor, so that the peeling of ozone is facilitated, cellulose is fully exposed, and cellulose hydrolysis is facilitated. The alkaline black liquor adsorbed by the XAD 16N macroporous adsorption resin still has a strong destructive effect, and can be recycled.
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911218430.XA CN112899325B (en) | 2019-12-03 | 2019-12-03 | Purification of alkali-ozone combined black liquor from lignocellulose pretreated by XAD 16N macroporous adsorption resin and its cyclic utilization |
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