CN104592529A - Novel lignin sulfonation technology - Google Patents
Novel lignin sulfonation technology Download PDFInfo
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Abstract
The invention relates to a novel water-soluble lignin sulfonate clean-production technology. The technology is characterized in that lignin recovered from high-density high-salinity pulping waste liquid and SO3 in an aprotic solvent undergo a direct and fast reaction to produce water-soluble lignin sulfonate. The technology fully develops a lignin raw material value, solves the difficulty and key problems of black liquor multistage integrated utilization, has good economic and ecological benefits, satisfies strategy requirements on vigorous development of natural renewable resources and sustainable development, has simple processes, allows mild conditions, realizes recycle of unreacted materials, does not produce toxic and side ions and solvent residue, can produce a product with wide purposes and has a large industrialized application prospect.
Description
Technical field
Patent of the present invention relates to a kind of lignin extraction and sulfonation novel process, belongs to the technical field of xylogen utilization and modification.
Background technology
Xylogen (Lignin) is the aromaticity polymkeric substance containing oxo phenylpropyl alcohol or derivatives thereof structural unit in a kind of unformed, molecular structure be extensively present in plant materials.The xylem (structure of a kind of responsible fortune water and mineral substance) of plant is containing a large amount of xylogen, and the hardness making xylem maintenance higher is to bear the weight of whole strain plant.
A large amount of xylogen is contained in paper-making industrial waste water and agricultural wastes, alkali lignin is the byproduct that acidifying is extracted from industrial black liquor of pulp making, but extract yield only has about 70%, and leaching process produces the hydrogen sulfide of stench, therefore the recycling of xylogen is few, the overwhelming majority is burned, and with only heat energy.Because the time of its natural degradation is longer, and exhaust emission water body and cause the wasting of resources, therefore, the exploitation of dominant resource xylogen just draw attention.About there are 1.4 hundred million tons of magma in the whole world every year for pulp and paper industry, can produce the black liquor containing 5,000 ten thousand tons of xylogen sodium simultaneously, is substantially burned at present or discharge.
Xylogen can be divided into 3 types: syringyl lignin (the syringyl lignin be polymerized by Syringa oblata Lindl. base propane structures alone, S-xylogen), guaiacyl xylogen (the guaiacyl lignin be polymerized by guaiacyl propane structures alone, G-xylogen) and by the p-hydroxy phenyl xylogen (hydroxy-phenyl lignin, H-xylogen) of p-hydroxyphenylpropane structure monomer polymerization.Lignin component is complicated, relative molecular mass distribution very wide (can from hundreds of to up to ten thousand), containing multiple functional group and chemical bonds such as ether, carbon-to-carbon double bond, the third methanol hydroxylethyl, phenolic hydroxyl group, carbonyl, methoxyl group, carboxyl and phenyl ring in molecule, it can react with electrophilic reagent, also can react with nucleophilic reagent, also can carry out oxidizing reaction, halogenating reaction, nitration reaction, Mannich reaction, diazotization reaction and graft copolymerization etc., xylogen is soluble in alkaline solution.
Under certain condition, sulfonic group can nitrogen hydrogen, hydroxyl, methoxyl group etc. on substituted benzene ring or side chain and become sulfonated lignin.Sulfonated lignin have nonpolar aromatic group, have again the sulfonic acid group of polarity, are a kind of water-soluble good anion surfactants, in faint yellow or tawny.Sulfonated lignin dissolve in the aqueous solution of various different pH value, and application is convenient, but is insoluble in ethanol, acetone and common organic solvents.
Because the reactive behavior of alkali lignin is poor, early stage sulfonation modifying all carries out under comparatively high temps and elevated pressures.United States Patent (USP) 2680113 reports and utilizes formaldehyde and S-WAT to carry out high temperature sulfonation to xylogen at 100 ~ 170 DEG C.Matsushita have studied and utilizes sodium hydroxymethane sulfonate sulfonation 2h under the condition of 150 DEG C, obtains the sulfonated lignin (Bioresource Technology, 2005,96:465-470) that sulphur content is 11.4%.This recent sulfonation reaction is all generally first activate alkali lignin, introduces the active function groups of easily reaction therein, then carries out sulfonation at ambient pressure.There is the problem that sulfonation time is long, sulfonation degree is low and product structure destroys in comparatively high temps and elevated pressures sulfonation; Under normal pressure, after first activation, sulfonation needs to add hazardous and noxious substances, affects quality product.
Novel process bamboo alkaline process is low cost, free of contamination process for cleanly preparing, alkali consumption is about 1/3rd of original production process, do not add the auxiliary agent such as sodium sulphite, anthraquinone, in production process, Mierocrystalline cellulose, lignin structure destroy little, and acid out reclaims xylogen than former technique advantageously.First, reclaim xylogen acid consumption and significantly reduce along with the minimizing of alkali number, macromole lignin molecule amount can be obtained; Secondly, acid out reclaims in xylogen process does not have the harmful rotten materials such as hydrogen sulfide to produce, and possible high-level efficiency, low cost are clean to be extracted.Finally, low salt concn and be conducive to microorganism growth without sulfide, can use Wastewater by Biochemical Treatment qualified discharge smoothly.
Based on the Research foundation in early stage, we have developed with SO
3be solvent as sulphonating agent, aprotic haloalkane, the method for sulfonated lignin is prepared at room temperature sulfonation.The method well overcomes the sulfonation that existing method exists and needs the problem of high temperature, high pressure, pollution, have that less investment, production cost are low, wide, the economic environmental protection of abundant raw material, end-use and ecological benefits outstanding feature, be one have economy, advance, practicality the another invention of great significance become.
Summary of the invention
The present invention proposes a kind of from pulping waste liquor optimize processing condition under acidifying reclaim alkali lignin, in non-protonic solvent, without acid binding agent existence under, with SO
3for sulfonated reagent, the short-cut method of synthesis sulfonated lignin.Namely from pulping waste liquor, acid out extracts xylogen, will containing finite concentration SO
3non-protonic solvent solution directly and alkali lignin stock suspension carry out inhomogeneous reaction, generation sulfonated lignin can be reacted very well under close to the lesser temps of normal temperature and in the reaction of 2 hours, namely reaction mixture obtains sulfonated lignin by the simple process such as precipitation, neutralization, and remaining solvent and the recyclable recycled of raw material are in next batch synthetic system.
This investigator finds in lignin recovery technical study, and raw material is the alkali lignin extracted in papermaking wastewater; Extraction process is with novel process black liquor of pulp making, and 50% sulfuric acid acid out, to pH value to 2.5, after stable, be put in the water-bath of 50 DEG C ~ 100 DEG C and be incubated 2.5h ~ 5h, make its sedimentation, then suction filtration, with distilled water wash, dry and obtain xylogen crude product.Xylogen directly uses SO
3sO during sulfonation
3dispersiveness and concentration very large on the impact of sulfonation effect.Directly SO is led in xylogen
3it is undesirable to there is sulfonation effect in the mode of gas, and reaction is only carried out on xylogen surface, and heat is difficult to remove, easily water suction dehydration carbonization, and sulfonation degree is difficult to the problems such as lifting.And non-protonic solvent is as easily remove 1,2-ethylene dichloride, methylene dichloride, propylene dichloride etc. can promote SO
3dissolve, not with SO
3react, be easily separated from reaction system, can effectively promote solid, liquid, gas state SO
3dissolve dispersion, form SO
3homogeneous phase solution.Because solvation is weak, SO
3in the aprotic solvent such as halohydrocarbon, activity is higher, reaction conditions milder.Ensure the SO of gas, liquid or solid form
3abundant dissolving and be dispersed in suspension xylogen xylogen solvent system in be react crucial thoroughly.
Take pulping waste liquor as raw material, certain holding temperature and under the time acid out extract xylogen, dry.Though sulfonated lignin can be obtained under comparatively high temps, in order to prevent carbonization and degraded, ensure output and the outward appearance of product, temperature of reaction 0 ~ 50 DEG C.SO
3with the consumption of solvent according to the requirement of product sulfonation degree adjustment in a big way, produce the SO of soluble lignin sulfonate
3usage quantity, with xylogen: SO
3(mass ratio) 1:0.5 ~ 4.Allow alkali lignin suspend in a solvent, more slowly pass into SO
3or drip the certain density SO be mixed with in advance
3solution, can supplement or apply mechanically recovered solvent and SO in reaction process
3raw material.Adopt and be mixed with SO in advance
3solution or limit pass into SO
3gas limit is reacted, and can supplement or apply mechanically recovered solvent SO in reaction process
3raw material, but control SO
3concentration be crucial, SO
3concentration range 0.5mol/L ~ 4mol/L.Though can obtain sulfonated lignin under the long period, power consumption is large and raw material may produce degraded, controls reaction times 0.5 ~ 8h.According to different sulfonation degree requirements, the condition such as its proportioning, temperature, time can also adjust.
Reaction terminates rear desolventizing and takes off SO
3solid mixture, through dissolve or dissolve neutralization, filter, precipitation can arrive sulfonated lignin salt crude product; Crude product or through purification after product can be used as cement water reducing agent, cement grinding aid, asphalt emulsifier, fuel dispersants, heavy crude thinner, oil recovery tensio-active agent, rubber reinforcing filler, slurries additive agent, resin adhesive, soil improvement agent and pesticide slow-releasing agent etc.
The outstanding advantages of novel process is as follows: 1. extraction and process for sulfonation are simply, mild condition, and less investment, can realize cleaner production; 2. high conversion and high yield can obtain product, and directly be converted into downstream derivative thing; 3. solvent boiling point is moderate, easy and SO
3remove together, capable of circulationly to apply mechanically; 4. not carbonization substantially, nontoxic secondary ion and dissolvent residual in product, by product is few, and purity is high; 5. abundant raw material source, product cost are low, of many uses, market potential large, have good industrialization prospect.
concrete implementation step
1. pulping waste liquor reclaims xylogen
From novel process pulping waste liquor, acid out extracts xylogen, and lignin recovery rate is analyzed, dry for standby.
2.SO
3the preparation of solution
By SO
3solid or gas add under cooling or pass in designated solvent, make it fully dissolve each other under stirring, be made into the SO of required reacting weight
3solution.
3. Sulphonation of Lignin
The material accurately taking oven dry, under room temperature or cooling and stirring, slowly drops into quantitative SO
3solution, keeps suitable temperature of reaction, stirring reaction certain hour.
4. post-treating method
After reaction terminates, product and 1,2-ethylene dichloride multi_layer extraction, alkali lye is neutralized to neutrality, dries and obtains sulfonated lignin crude product.
5. yield judges the analysis with product
The dry laggard row element analysis of crude product dialysis, obtains product sulphur content.
Form 1 product analysis project and analytical procedure
Embodiment
The present invention can be further described with nonlimiting examples hereinafter.Following embodiment reflects pulping waste liquor and extracts xylogen implementation result, and different ratio, SO
3the implementation result of sulfonated lignin under the condition of concentration, temperature, time, raw material, solvent.
Embodiment 1
Get novel process black liquor of pulp making 100g in 500mL beaker, open induction stirring, add 50% sulfuric acid while stirring, adjust ph to 2.5, after stable, be put in the water-bath of 100 DEG C and be incubated 5h.Make its sedimentation, then suction filtration, with distilled water wash, dry and obtain xylogen crude product.Black liquor and filtrate absorbancy before ultra-violet analysis acid out, measuring lignin recovery rate is 97%.
Embodiment 2
Get novel process black liquor of pulp making 100g in 500mL beaker, open induction stirring, add 50% sulfuric acid while stirring, adjust ph to 2.5, after stable, be put in the water-bath of 50 DEG C and be incubated 2.5h.Make its sedimentation, then suction filtration, with distilled water wash, dry and obtain xylogen crude product.Black liquor and filtrate absorbancy before ultra-violet analysis acid out, measuring lignin recovery rate is 90%.
Embodiment 3
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 2.56g xylogen, control bath temperature 20 DEG C, under whipped state, slowly drip the SO of preparation
3solution 8ml, reaction 2h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 4
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.32g xylogen, add 7ml1,2-ethylene dichloride, control bath temperature 0 DEG C, under whipped state, slowly drip the SO of preparation
3solution 1ml, reaction 2h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 5
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.16g xylogen, add 14ml1,2-ethylene dichloride, control bath temperature 20 DEG C, under whipped state, slowly drip the SO of preparation
3solution 2ml, reaction 2h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 6
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.32g xylogen, add 7ml1,2-ethylene dichloride, control bath temperature 20 DEG C, under whipped state, slowly drip the SO of preparation
3solution 1ml, reaction 2h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 7
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.32g xylogen, add 7ml1,2-ethylene dichloride, control bath temperature 20 DEG C, under whipped state, slowly drip the SO of preparation
3solution 1ml, reaction 8h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 8
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.32g xylogen, add 7ml1,2-ethylene dichloride, control bath temperature 50 DEG C, under whipped state, slowly drip the SO of preparation
3solution 1ml, reaction 2h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 9
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.64g xylogen, add 7ml1,2-ethylene dichloride, control bath temperature 20 DEG C, under whipped state, slowly drip the SO of preparation
3solution 1ml, reaction 2h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 10
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.32g xylogen, add 7ml1,2-ethylene dichloride, control bath temperature 20 DEG C, under whipped state, slowly drip the SO of preparation
3solution 1ml, reaction 0.5h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product.
Embodiment 11
By solid or gas SO
3, add or pass into cooling 1,2-ethylene dichloride in be made into the SO of 4mol/L
3/ 1,2-dichloroethane solution.Get 0.32g xylogen, add 21ml1,2-ethylene dichloride, control bath temperature 30 DEG C, under whipped state, slowly drip the SO of preparation
3solution 3ml, reaction 1h.Reaction terminates rear separation solvent, adds in the NaOH of 1mol/L and sulphur trioxide, and to pH=8 ~ 10, alcohol settling, dialysis 48h, concentrate dialysate, 60 DEG C of vacuum-dryings obtain product, to product Infrared Characterization.
Embodiment 12
Normal temperature and pressure formaldehyde, S-WAT sulfonation system related experiment take 50g alkali and slightly carry xylogen solid, add 2.5wt%NaOH solution 200g, are heated to 50 DEG C while stirring; Add the aqueous solution 25g of 15g ammonium persulphate, 2.5g ferrous sulfate, being slowly warming up to 75 DEG C carries out free radical cracking reaction simultaneously, insulation 30min; Under the state stirred, drip 7g formaldehyde (35 ~ 37%wt), isothermal reaction 2h; Continue to be warming up to 95 DEG C, slowly add 25g sodium sulphite anhydrous 99.3, isothermal reaction 3h; 10%wt sulphuric acid soln regulates pH to 3, centrifugal removing insolubles; Add 2.5wt%NaOH solution and regulate pH to 6 (dialysis tubing pH scope 5 ~ 9), dialysis treatment, 60 DEG C of dryings.
Product ultimate analysis, Infrared Characterization, all prove that product is sulfonated lignin.Coherent element analysis and characterization is shown in accompanying drawing 1 in table 2,3, FI-IR, and interpretation of result is as follows:
Form 2 Sulphonation of Lignin elemental analysis
The different method of sulfonating of form 3 compares
Along with sulfonic introducing, product water dissolubility increases.Water-soluble products FT-IR spectrogram is shown in accompanying drawing 1, therefrom analyzes known: comparatively raw material alkali lignin, has occurred the new peak of 1140-1150 in product, and this is sulfonic acid group characteristic peak.
Accompanying drawing illustrates:
Accompanying drawing 1 is the FT-IR spectrogram for product in embodiment 10.
Claims (10)
1. the present invention proposes a kind of from pulping waste liquor optimize processing condition under acidifying reclaim alkali lignin, in non-protonic solvent, without acid binding agent existence under, with SO
3for sulfonated reagent, the short-cut method of synthesis sulfonated lignin; Namely from pulping waste liquor, acid out extracts xylogen, will containing finite concentration SO
3non-protonic solvent solution directly and alkali lignin stock suspension carry out inhomogeneous reaction, generation sulfonated lignin can be reacted very well under close to the lesser temps of normal temperature and in the reaction of 2 hours, namely reaction mixture obtains sulfonated lignin by the simple process such as precipitation, neutralization, and remaining solvent and the recyclable recycled of raw material are in next batch synthetic system.
2. method according to claim 1, wherein non-protonic solvent to promote SO
3dissolve, not with SO
3reaction, the solvent be easily separated from reaction system.
3. the method according to any one of claim 1-2, with 1, the 2-ethylene dichloride, the methylene dichloride that easily remove in solvent selection, propylene dichloride is preferred.
4. method according to claim 1, its Raw is the alkali lignin extracted in papermaking wastewater; Extraction process is with novel process black liquor of pulp making, and 50% sulfuric acid acid out, to pH value to 2.5, after stable, be put in the water-bath of 50 DEG C ~ 100 DEG C and be incubated 2.5h ~ 5h, make its sedimentation, then suction filtration, with distilled water wash, dry and obtain xylogen crude product.
5. method according to claim 1, though can obtain sulfonated lignin under comparatively high temps, in order to prevent carbonization and degraded, ensures output and the outward appearance of product, temperature of reaction 0 ~ 50 DEG C.
6. method according to claim 1, SO
3with the consumption of solvent according to the requirement of product sulfonation degree adjustment in a big way, produce the SO of soluble lignin sulfonate
3usage quantity, xylogen: SO
3(mass ratio) 1:0.5 ~ 4.
7. method according to claim 1, adopts and is mixed with SO in advance
3solution or limit pass into SO
3gas limit is reacted, and can supplement or apply mechanically recovered solvent SO in reaction process
3raw material is all suitable feed way, but control SO
3concentration be crucial, SO
3concentration range 0.5mol/L ~ 4mol/L.
8. want the method described in 7 according to right, preferred scheme is: allow alkali lignin suspend in a solvent, more slowly pass into SO
3or drip the certain density SO be mixed with in advance
3solution, can supplement or apply mechanically recovered solvent and SO in reaction process
3raw material.
9. method according to claim 1, though can obtain sulfonated lignin under the long period, power consumption is large and raw material may produce degraded, controls reaction times 0.5 ~ 8h.
10. method according to claim 1, reaction terminates rear desolventizing and takes off SO
3solid mixture, through dissolve or dissolve neutralization, filter, precipitation can arrive sulfonated lignin salt crude product; Crude product or through purification after product can be used as cement water reducing agent, cement grinding aid, asphalt emulsifier, fuel dispersants, heavy crude thinner, oil recovery tensio-active agent, rubber reinforcing filler, slurries additive agent, resin adhesive, soil improvement agent and pesticide slow-releasing agent etc.
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| CN105541901A (en) * | 2015-12-21 | 2016-05-04 | 合肥星宇化学有限责任公司 | Preparation method for 2,4-dichloro-5-nitrophenyl phosphotriester |
| CN107814952A (en) * | 2017-10-18 | 2018-03-20 | 暨南大学 | A kind of lignin nanoparticle and the synchronous preparation method for carrying medicine |
| CN109650535A (en) * | 2019-01-02 | 2019-04-19 | 齐鲁工业大学 | A kind of application of lignin and its derivative charcoal in anaerobic digestion |
| CN109792053A (en) * | 2016-09-30 | 2019-05-21 | 株式会社杰士汤浅国际 | Lead storage battery |
| CN111072991A (en) * | 2019-12-24 | 2020-04-28 | 鞍钢集团矿业有限公司 | Preparation method of bio-based sulfonate for improving saline-alkali soil |
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| CN115975216A (en) * | 2021-10-14 | 2023-04-18 | 中国科学院大连化学物理研究所 | Low-temperature hydrophilic modification method for lignin |
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| CN103360499A (en) * | 2012-04-11 | 2013-10-23 | 厦门大学 | Simple synthesis process of cellulose sulfate |
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| CN102140173A (en) * | 2010-12-28 | 2011-08-03 | 新疆天宏纸业股份有限公司 | Method for producing sodium lignin sulfonate by using black liquor from pulping of reed containing sodium sulfite |
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| CN105541901A (en) * | 2015-12-21 | 2016-05-04 | 合肥星宇化学有限责任公司 | Preparation method for 2,4-dichloro-5-nitrophenyl phosphotriester |
| CN105541901B (en) * | 2015-12-21 | 2018-08-28 | 合肥星宇化学有限责任公司 | A kind of preparation method of bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- |
| CN109792053A (en) * | 2016-09-30 | 2019-05-21 | 株式会社杰士汤浅国际 | Lead storage battery |
| US11424452B2 (en) | 2016-09-30 | 2022-08-23 | Gs Yuasa International Ltd. | Lead-acid battery |
| CN107814952A (en) * | 2017-10-18 | 2018-03-20 | 暨南大学 | A kind of lignin nanoparticle and the synchronous preparation method for carrying medicine |
| CN107814952B (en) * | 2017-10-18 | 2020-03-17 | 暨南大学 | Lignin nanoparticle and preparation method of synchronous drug loading |
| CN109650535A (en) * | 2019-01-02 | 2019-04-19 | 齐鲁工业大学 | A kind of application of lignin and its derivative charcoal in anaerobic digestion |
| CN109650535B (en) * | 2019-01-02 | 2022-03-25 | 齐鲁工业大学 | Application of lignin and derived carbon thereof in anaerobic digestion |
| CN111072991A (en) * | 2019-12-24 | 2020-04-28 | 鞍钢集团矿业有限公司 | Preparation method of bio-based sulfonate for improving saline-alkali soil |
| CN111097790A (en) * | 2019-12-24 | 2020-05-05 | 鞍钢集团矿业有限公司 | Method for repairing saline-alkali soil by using salt discharge pipe, iron tailings and modifier |
| CN115975216A (en) * | 2021-10-14 | 2023-04-18 | 中国科学院大连化学物理研究所 | Low-temperature hydrophilic modification method for lignin |
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