CN104592529B - A kind of Sulphonation of Lignin new process - Google Patents
A kind of Sulphonation of Lignin new process Download PDFInfo
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- CN104592529B CN104592529B CN201310526676.XA CN201310526676A CN104592529B CN 104592529 B CN104592529 B CN 104592529B CN 201310526676 A CN201310526676 A CN 201310526676A CN 104592529 B CN104592529 B CN 104592529B
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Abstract
The present invention relates to a kind of high salinity pulping waste liquors of high concentration to recycle lignin, in non-protonic solvent, with SO3With the direct fast reaction of raw material of pulping waste liquor recycling lignin, the new process for cleanly preparing of synthesizing water-solubility lignosulfonates.This technique sufficiently develops the raw material value of lignin, solve the difficult point and Important Problems of the comprehensive utilization of black liquor multistage, with good economy and ecological benefits, meet the strategic requirement of Devoting Major Efforts To Developing natural reproducible resource and sustainable development, there is simple process, mild condition, unreacted material is recyclable to be applied, nontoxic pair ion and dissolvent residual, product purpose is extensive, has huge industrial application prospect.
Description
Technical field
The invention patent relates to a kind of lignin extraction and sulfonation new processes, belong to the technology that lignin is utilized and is modified and lead
Domain.
Background technique
Lignin (Lignin) is to contain oxo in a kind of unformed, molecular structure being widely present in plant
The armaticity polymer of phenylpropanol or derivatives thereof structural unit.A kind of xylem (structure of responsible fortune water and minerals of plant
Make) containing a large amount of lignin, so that xylem is maintained higher hardness to undertake the weight of whole plant.
Contain a large amount of lignin in paper-making industrial waste water and agricultural wastes, alkali lignin is from industrial black liquor of pulp making
It is acidified the byproduct extracted, but extract yield only has 70% or so, and extraction process generates the hydrogen sulfide of stench, therefore
The recycling of lignin is few, and the overwhelming majority is incinerated, with only thermal energy.Since the time of its natural degradation is longer,
And exhaust emission water body and result in waste of resources, therefore, the development and utilization of dominant resource lignin just draw attention.Entirely
There are about 1.4 hundred million tons of magma to be used for pulp and paper industry every year for ball, while can generate the black liquor containing 50,000,000 tons of lignin sodium, mesh
It is preceding to be incinerated or discharge substantially.
Lignin can be divided into 3 seed types: the syringyl lignin being polymerized by lilac base propane structures alone
(syringyl lignin, S- lignin), the guaiacyl lignin being polymerized by guaiacyl propane structures alone
(guaiacyl lignin, G- lignin) and the p- hydroxy benzenes sill as made of p- hydroxyphenylpropane structure monomer polymerization
Quality (hydroxy-phenyl lignin, H- lignin).Lignin component is complicated, and relative molecular mass distribution is very wide (can
From several hundred to up to ten thousand), in molecule containing ether, carbon-to-carbon double bond, the third methanol hydroxylethyl, phenolic hydroxyl group, carbonyl, methoxyl group, carboxyl and
A variety of functional groups such as phenyl ring and chemical bond, it can be reacted with electrophilic reagent, can also be reacted with nucleopilic reagent,
Under certain condition, sulfonic group can become wood with nitrogen hydrogen, hydroxyl, methoxyl group on substituted benzene ring or side chain etc.
Mahogany sulfonate.Lignosulfonates have nonpolar aromatic group, and have polar sulfonic acid group, are a kind of water-soluble
Property good anionic surfactant, be in faint yellow or yellowish-brown.Lignosulfonates dissolve in the water of various different pH value
In solution, using convenience, but insoluble in ethyl alcohol, acetone and common organic solvents.
Since the reactivity of alkali lignin is poor, the sulfonation modifying of early stage is all under higher temperature and elevated pressures
It carries out.United States Patent (USP) 2680113, which is reported, carries out high temperature to lignin using formaldehyde and sodium sulfite at 100~170 DEG C
Sulfonation.Matsushita has studied using sodium hydroxymethane sulfonate sulfonation 2h under conditions of 150 DEG C, and having obtained sulfur content is
11.4% lignosulfonates (Bioresource Technology, 2005,96:465-470).This recent sulfonating reaction
Alkali lignin is typically first activated, introduces the active function groups for being easy reaction inside it, then carry out sulfonation under normal pressure.
Higher temperature and elevated pressures sulfonation have that sulfonation time is long, sulfonation degree is low and product structure destroys；It first lives under normal pressure
Sulfonation needs that poisonous and harmful substance is added after change, influences product quality.
New process bamboo soda pulping process is low cost, free of contamination process for cleanly preparing, and alkali consumption is original production process
One third or so does not add the auxiliary agents such as vulcanized sodium, anthraquinone, and cellulose, lignin structure destroy small, acid in production process
Analysis recycling lignin is advantageously than original process.Firstly, recycling lignin acid consumption is greatly decreased with the reduction of alkali number,
Macromolecular lignin molecule amount can be obtained；Secondly, there is no the production of the harmful rottens substance such as hydrogen sulfide during acid out recycling lignin
Raw, possible high efficiency, low cost cleaning are extracted.Finally, low salt concn and without sulfide be conducive to microorganism growth, Ke Yishun
Utilize Wastewater by Biochemical Treatment qualified discharge.
Research foundation based on early period, we have developed with SO3It is solvent as sulfonating agent, aprotic alkyl halide,
The method that sulfonation prepares lignosulfonate at room temperature.This method overcomes sulfonation existing for existing method well needs high temperature, height
The problem of pressure, pollution, with small investment, production cost is low, abundant raw material, product purpose is wide, economic and environment-friendly and ecological benefits are aobvious
The characteristics of work is economical, advanced, practicability an another invention of great significance at.
Summary of the invention
The invention proposes a kind of from alkali lignin is recycled in acidification under the process conditions of optimization in pulping waste liquor, non-
In protonic solvent, in the presence of no acid binding agent, with SO3For sulfonated reagent, the short-cut method of lignosulfonates is synthesized.I.e. from
Acid out extracts lignin in pulping waste liquor, will contain a certain concentration SO3Non-protonic solvent solution directly with alkali lignin raw material
Suspension carries out heterogeneous reaction, can react very well raw under the lower temperature close to room temperature and in reaction in 2 hours or so
At lignosulfonate, reaction mixture obtains lignosulfonates, remaining solvent by simple process such as precipitation, neutralizations
Recycled can be recycled in next group synthetic system with raw material.
This researcher has found that raw material is the alkali lignin extracted in papermaking wastewater in lignin recovery technical study；It mentions
Taking technique is put in 50 DEG C~100 DEG C of water-bath after stablizing with new process black liquor of pulp making, 50% sulfuric acid acid out to pH value to 2.5
Middle heat preservation 2.5h~5h, makes its sedimentation, then filters, and is washed with distilled water, lignin crude product obtained by drying.Lignin is direct
Use SO3SO when sulfonation3Dispersibility and influence of the concentration to sulfonation effect it is very big.The directly logical SO into lignin3The side of gas
There are sulfonation effect is undesirable, reaction only carries out on lignin surface formula, and heat is difficult to remove, and is easy water suction dehydration carbonization,
Sulfonation degree is difficult to the problems such as being promoted.And non-protonic solvent is such as easy 1,2- dichloroethanes, the methylene chloride of removing, dichloro third
Alkane etc. can promote SO3Dissolution, not with SO3Reaction is easily separated from reaction system, can effectively facilitate solid, liquid, gas state SO3It is molten
Solution dispersion, forms SO3Homogeneous phase solution.Since solvation is weak, SO3Activity is higher in the aprotic solvent such as halogenated hydrocarbons, instead
Answer condition milder.Guarantee the SO of gas, liquid or solid form3Sufficiently dissolve and be dispersed in suspension lignin lignin
It is that reaction is thoroughly crucial in dicyandiamide solution.
Using pulping waste liquor as raw material, acid out extracts lignin, drying under certain holding temperature and time.Under higher temperature
Though lignosulfonates can be obtained, it is carbonized and degrades in order to prevent, guarantee the yield and appearance of product, reaction temperature 0~50
℃。SO3Dosage with solvent produces soluble lignin sulfonate according to the large range of adjusting of requirement of product sulfonation degree
SO3Usage amount, with lignin: SO3(mass ratio) 1:0.5~4.It allows alkali lignin to suspend in a solvent, then is slowly introducing SO3
Or the certain density SO being configured in advance is added dropwise3Solution can supplement or apply recovered solvent and SO in reaction process3
Raw material.SO is configured to using preparatory3Solution or side are passed through SO3Gas side is reacted, and can supplement or apply recycling in reaction process
Solvent SO3Raw material, but control SO3Concentration be crucial, SO3Concentration range 0.5mol/L~4mol/L.Under long period
Though lignosulfonates can be obtained, there may be degradations for the big and raw material that consumes energy, and control 0.5~8h of reaction time.According to difference
Sulfonation degree requirement, the conditions such as proportion, temperature, time can also adjust.
Desolventizing takes off SO after reaction3Solid mixture, dissolved or dissolved neutralization, filtering, precipitating can arrive it is wooden
Plain sulfonate salt crude product；Crude product or the product after purification can be used as cement water reducing agent, cement grinding aid, pitch cream
Agent, heavy crude thinner, recovers the oil and uses surfactant, rubber reinforcing filler, slurries additive agent, resin gluing at fuel dispersants
Agent, soil conditioner and pesticide slow-releasing agent etc..
The outstanding advantages of new process are as follows: 1. extracting and process for sulfonation is simple, mild condition, small investment is, it can be achieved that cleaning
Production；2. high conversion and product can be obtained in high yield, and it is directly converted into downstream derivative object；3. solvent boiling point is moderate, easily
With SO3It removes together, it is recyclable to apply；4. not being carbonized substantially, nontoxic pair ion and dissolvent residual in product, by-product is few, pure
Degree is high；5. raw material sources are abundant, product cost is low, widely used, great market potential, there is good industrialization prospect.
Specific implementation step
1. pulping waste liquor recycles lignin
Acid out extracts lignin from new process pulping waste liquor, and the analysis of lignin recovery rate is dried for standby.
2.SO3The preparation of solution
By SO3Solid or gas be added or be passed through in designated solvent under cooling, so that it is sufficiently dissolved each other under stirring, match
At the SO of required reacting dose3Solution.
3. Sulphonation of Lignin
The material of drying is accurately weighed under room temperature or cooling and stirring, slowly puts into quantitative SO3Solution keeps suitable
Reaction temperature, be stirred to react certain time.
4. post-processing approach
After reaction, product and 1,2- dichloroethanes multi_layer extraction, lye are neutralized to neutrality, and drying obtains lignin
Sulfonate crude product.
5. the analysis of yield judgement and product
The dry laggard row element analysis of crude product dialysis, obtains product sulfur content.
1 product analysis project of table and analysis method
Detailed description of the invention:
Attached drawing 1 is in embodiment 10 be product FT-IR spectrogram.
Specific embodiment
The available nonlimiting examples hereinafter of the present invention are further described.Embodiment below reflects system
Pulp waste extracts lignin implementation result and different ratio, SO3Sulphur under conditions of concentration, temperature, time, raw material, solvent
Change the implementation result of lignin.
Embodiment 1
It takes new process black liquor of pulp making 100g in 500mL beaker, opens electromagnetic agitation, 50% sulfuric acid is added while stirring,
PH value is adjusted to 2.5, after stablizing, is put in 100 DEG C of water-bath and keeps the temperature 5h.Make its sedimentation, then filters, be washed with distilled water,
Lignin crude product obtained by drying.Black liquor and filtrate absorbance before ultra-violet analysis acid out, measurement lignin recovery rate are 97%.
Embodiment 2
It takes new process black liquor of pulp making 100g in 500mL beaker, opens electromagnetic agitation, 50% sulfuric acid is added while stirring,
PH value is adjusted to 2.5, after stablizing, is put in 50 DEG C of water-bath and keeps the temperature 2.5h.Make its sedimentation, then filter, is washed with distillation
It washs, lignin crude product obtained by drying.Black liquor and filtrate absorbance before ultra-violet analysis acid out, measurement lignin recovery rate are 90%.
Embodiment 3
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.2.56g lignin is taken, 20 DEG C of bath temperature is controlled, under stirring, the SO of preparation is slowly added dropwise3Solution
8ml reacts 2h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide, until pH=8~10, ethyl alcohol is heavy
It forms sediment, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 4
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.32g lignin is taken, 7ml1 is added, 2- dichloroethanes controls 0 DEG C of bath temperature, under stirring, slowly
The SO prepared is added dropwise3Solution 1ml reacts 2h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide, until
PH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 5
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.16g lignin is taken, 14ml1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 2ml reacts 2h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide,
To pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 6
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.32g lignin is taken, 7ml1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 1ml reacts 2h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide,
To pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 7
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.32g lignin is taken, 7ml1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 1ml reacts 8h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide,
To pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 8
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.32g lignin is taken, 7ml1 is added, 2- dichloroethanes controls 50 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 1ml reacts 2h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide,
To pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 9
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.64g lignin is taken, 7ml1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 1ml reacts 2h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide,
To pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 10
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.32g lignin is taken, 7ml1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 1ml reacts 0.5 h.Solvent is separated after reaction, and the NaOH of 1mol/L is added to neutralize three oxidations
Sulphur, until pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
Embodiment 11
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- bis-
Chloroethanes solution.0.32g lignin is taken, 21ml1 is added, 2- dichloroethanes controls 30 DEG C of bath temperature, under stirring, slowly
It is slow that the SO prepared is added dropwise3Solution 3ml reacts 1h.Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide,
To pH=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product, to product IR Characterization.
Embodiment 12
Normal temperature and pressure formaldehyde, sodium sulfite sulfonation system related experiment weigh 50g alkali and slightly mention lignin solid, are added
2.5wt%NaOH solution 200g, is heated to 50 DEG C while stirring；The aqueous solution of 15g ammonium persulfate, 2.5g ferrous sulfate is added
25g, while 75 DEG C of progress free radical cracking reactions are to slowly warm up to, keep the temperature 30min；While stirring, 7g formaldehyde is added dropwise
(35~37%wt), isothermal reaction 2h；95 DEG C are continuously heating to, 25g anhydrous sodium sulfite, isothermal reaction 3h are slowly added to；
10%wt sulfuric acid solution adjusts pH to 3, is centrifuged off insoluble matter；2.5wt%NaOH solution is added to adjust (the bag filter pH model of pH to 6
Enclose 5~9), dialysis treatment, 60 DEG C of dryings.
Product elemental analysis, IR Characterization, proof product are lignosulfonates.Coherent element analysis and characterization is shown in Table 2,
3, FI-IR see attached drawing 1, and interpretation of result is as follows:
2 Sulphonation of Lignin elemental analysis of table
The different method of sulfonating of table 3 compare
With sulfonic introducing, product water solubility increases.Water-soluble products FT-IR spectrogram is shown in attached drawing 1, and therefrom analysis can
Know: occurring the new peak of 1140-1150 for raw material alkali lignin, in product, this is sulfonic acid group characteristic peak.
Claims (1)
1. a kind of method for synthesizing lignosulfonates, acid out extracts lignin from pulping waste liquor, and specific method is will to make
Black liquor 50% sulfuric acid acid out to pH value to 2.5 is starched, after stablizing, heat preservation 2.5h~5h in 50 DEG C~100 DEG C of water-bath is put in, makes
It is settled, and is then filtered, is washed with distilled water, dries to obtain lignin crude product；Then lignosulfonates are synthesized, it is specific using such as
Lower method:
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- dichloroethanes
Solution；0.16g lignin is taken, 14ml 1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, is slowly added dropwise
The SO of preparation3Solution 2ml reacts 2h；Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide, until pH=
8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product；Alternatively,
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- dichloroethanes
Solution；0.32g lignin is taken, 7ml 1 is added, 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, is slowly added dropwise
The SO of preparation3Solution 1ml reacts 8h；Solvent is separated after reaction, is added in the NaOH of 1mol/L and sulfur trioxide, until pH=8
~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product；Alternatively,
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- dichloroethanes
Solution takes 0.32g lignin, and 7ml 1 is added, and 2- dichloroethanes controls 20 DEG C of bath temperature, under stirring, is slowly added dropwise
The SO of preparation3Solution 1ml reacts 0.5h, separates solvent after reaction, add in the NaOH of 1mol/L and sulfur trioxide, until pH
=8~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product；Alternatively,
By solid or gas SO3, it is added or is passed through the SO that 4mol/L is made into cooling 1,2- dichloroethanes3/ 1,2- dichloroethanes
Solution takes 0.32g lignin, and 21ml 1 is added, and 2- dichloroethanes controls 30 DEG C of bath temperature, under stirring, is slowly added dropwise
The SO of preparation3Solution 3ml reacts 1h, separates solvent after reaction, add in the NaOH of 1mol/L and sulfur trioxide, until pH=8
~10, ethanol precipitation, dialyse 48h, and concentrate dialysate, 60 DEG C are dried in vacuo to obtain product.
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| 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- |
| JP6775764B2 (en) * | 2016-09-30 | 2020-10-28 | 株式会社Ｇｓユアサ | Lead-acid battery |
| CN107814952B (en) * | 2017-10-18 | 2020-03-17 | 暨南大学 | Lignin nanoparticle and preparation method of synchronous drug loading |
| 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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| CN103360499A (en) * | 2012-04-11 | 2013-10-23 | 厦门大学 | Simple synthesis process of cellulose sulfate |
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