CN105885058A - Method utilizing crop straws to prepare sodium lignosulfonate - Google Patents
Method utilizing crop straws to prepare sodium lignosulfonate Download PDFInfo
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- CN105885058A CN105885058A CN201410605746.5A CN201410605746A CN105885058A CN 105885058 A CN105885058 A CN 105885058A CN 201410605746 A CN201410605746 A CN 201410605746A CN 105885058 A CN105885058 A CN 105885058A
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- methylimidazole
- lignin
- straw
- ionic liquid
- solvent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method utilizing crop straws to prepare sodium lignosulfonate. The method comprises the following steps: washing, drying, and grinding crop straws; adding an ionic liquid, a solvent, and crop straw particles into a reactor to carry out reactions; after reactions, filtering the mixture, recovering the solvent; adding deionized water into the filtered substances so as to precipitate the lignin, separating and drying lignin; preparing suspension liquid from the obtained lignin, adjusting the pH value, adding sodium sulfite, carrying out reactions, after reactions, filtering; concentrating the filtrate, and performing spray-drying to obtain sodium lignosulfonate. The straws are processed by ionic liquid and solvent, thus the utilization rate of lignin is largely improved; the ionic liquid and solvent can be recovered easily, the cost is largely reduced; ionic liquid is use to replace liquid alkali; compared with the prior art, the prepared sodium lignosulfonate has the advantages of high purity, simple steps, and low cost, and no environmental pollution is generated.
Description
Technical field
The present invention relates to a kind of method preparing sodium lignin sulfonate, a kind of method utilizing agricultural crop straw to prepare sodium lignin sulfonate, belong to
In natural macromolecular material and chemical technology field.
Background technology
Agricultural crop straw is the abundantest in China, and wherein, Caulis et Folium Oryzae, wheat stalk and corn straw are China three grande culture thing straws.Currently, straw
The highest at the producing level of China, benefit is also at than relatively low level.Common straw utilization mode specifically includes that 1, directly burns, this
Sample is not only wasted resource, is destroyed Soil structure, and easily causes air pollution, even the serious consequence such as initiation fire；2, chopping and returning,
Straw-returning is the most bad levels land, and also easily causes the dead Seedling of Soil ventilation, and water percolating capacity of irrigating the fields is big, is also easily generated pest and disease damage simultaneously；3, as feedstuff,
It is worth due to straw nutrition and utilization rate is relatively low, add the reduction of dirty swine feed price and the raising of efficiency so that the value of this mode is relatively low.Agriculture
Crop material is mainly composed of lignocellulose, it is possible to effectively utilize lignocellulose, for solving environmental pollution, food shortages and energy crisis
It is of great immediate significance.
Lignocellulose is the raw material with cellulose, hemicellulose and lignin as main component, wherein lignin can by modified, process, compounding
Preparing a series of lignin product etc. method, sodium lignin sulfonate is exactly one of them.Sodium lignin sulfonate as a kind of anion surfactant,
Can as purificant, dispersant, high alkalinity additive, antirust agent, antistatic additive, emulsifying pour depressor, disappear wax wax-proofing agent etc..Relevant utilize farming
The report that thing straw prepares sodium lignin sulfonate is fewer, and Chinese patent CN103408671A provides one, and to utilize agricultural crop straw to produce wooden
The method of element sodium sulfonate, it processes agricultural crop straw mainly by sodium hydroxide and sodium sulfite mixed solution, but during base extraction straw can be
A part of lignin is degraded, and part hemicellulose also can be made to decompose, and loss is relatively big, simultaneously base extraction there is also reagent reclaim, neutralize with
And the problem such as washing, these problems can be to environment.
Summary of the invention
For solving an above existing difficult problem, the invention discloses a kind of method utilizing crops straw to prepare sodium lignin sulfonate, use ionic liquid with
Lignocellulose in straw is effectively separated by dicyandiamide solution, is then modified, the lignin after separating simultaneously to ionic liquid and solvent
Reclaim, be greatly saved cost, and environment is not resulted in any pollution.
A kind of method utilizing agricultural crop straw to prepare sodium lignin sulfonate, comprises the following steps:
The first step: agricultural crop straw is washed, dries, be ground into 3-10mm stalk particle.
Second step: ionic liquid, solvent, agricultural crop straw granule being added in reactor, heated and stirred mixture 1～24 is little at 90～180 DEG C
Time, wherein mixture intermediate ion liquid mass fraction is 0.10～0.76；The mass fraction of agricultural crop straw is 0.05～0.34；The quality of solvent is divided
Number is 0.19～0.90.
Described ionic liquid includes: 1-butyl-3-Methylimidazole. villaumite, 1-ethyl-3-methylimidazole villaumite, 1-pi-allyl-3-Methylimidazole. chlorine
Salt, 1-benzyl-3-Methylimidazole. villaumite, 1-hexyl-3-Methylimidazole. villaumite, 1-butyl-3-Methylimidazole. dimethyl phosphate salt, 1-ethyl-3-first
Base imidazoles dimethyl phosphate salt, 1-pi-allyl-3-Methylimidazole. dimethyl phosphate salt, 1-benzyl-3-Methylimidazole. dimethyl phosphate salt, 1-hexyl-3
Methylimidazole. dimethyl phosphate salt, 1-butyl-3-Methylimidazole. trifluoromethyl sulfonic acid, 1-ethyl-3-methylimidazole trifluoromethyl sulfonic acid, 1-alkene
Propyl group-3-Methylimidazole. trifluoromethyl sulfonic acid, 1-benzyl-3-Methylimidazole. trifluoromethyl sulfonic acid, 1-hexyl-3-Methylimidazole. trifluoromethyl sulphur
Hydrochlorate, 1-butyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazole Methylsulfate, 1-pi-allyl-3-Methylimidazole. methylsulfuric acid
Salt, 1-benzyl-3-methylimidazolium methylsulfate, 1-hexyl-3-methylimidazolium methylsulfate, 1-butyl-3-carboxymethyl imidazoles dimethyl phosphate
Salt, 1-ethyl-3-carboxymethyl imidazoles dimethyl phosphate salt, 1-benzyl-3-carboxymethyl imidazoles trifluoromethyl sulfonic acid, 1-hexyl-3-carboxymethyl imidazoles
One or more in trifluoromethyl sulfonic acid；
Described solvent includes: one or more in water, methanol, ethanol, acetonitrile, glycerol, isopropanol；
Described agricultural crop straw includes: in corn straw, Caulis et Folium Oryzae, wheat stalk, Caulis Sacchari sinensis straw, cotton stalk, potato class straw, oil plant straw
One or more.
3rd step: filtered by the mixture in reactor, collects filtrate, removes solvent, recycles；And add in residue and to go in a large number
Ionized water, is settled out lignin, separates and obtains lignin after drying；Continue distillation and remove water, ionic liquid can be reclaimed.The wherein receipts of lignin
Rate is 10.15%～32.19%；The quality of deionized water is 1-10 times of ionic liquid quality.
4th step: lignin obtained above is made into the suspension that mass concentration is 15wt%～40wt%, and regulates the pH value of suspension extremely
4.5～8.5.
5th step: add sodium sulfite in above-mentioned suspension, at 105 DEG C～150 DEG C, stirring reaction 2～10 hours, filter after reaction, are filtered
Liquid.Wherein sodium sulfite is (1.5～4) mmol/g with the ratio of lignin.
6th step: the filtrate of gained is concentrated and is spray-dried, prepares sodium lignin sulfonate.
Beneficial effect: the present invention uses ionic liquid and solvent to process straw and is greatly improved the utilization rate of lignin: ionic liquid and solvent are easily recycled,
Greatly reduce cost；This operation utilizes ionic liquid to process, rather than alkali liquor, and existing method ratio, sodium lignin sulfonate purity prepared by the present invention is high,
Operation is simple, with low cost and environment does not results in any pollution.
Accompanying drawing explanation
Fig. 1 is the SEM figure of corn straw after ionic liquid and solvent process 1 hour in embodiment 1.
Detailed description of the invention
In conjunction with below embodiment, the present invention is described in further details, but is not limiting as the present invention.
Embodiment 1
A kind of method utilizing agricultural crop straw to prepare sodium lignin sulfonate, comprises the following steps:
Being washed by corn straw, be dried, powder becomes the stalk particle of 3～10mm, then by 50g1-butyl-3-Methylimidazole. trifluoromethyl sulfonic acid,
20g acetonitrile, 30g corn stalk pellets join in reactor, and at 160 DEG C, heated and stirred is reacted 2 hours, after reaction terminates, by reactor
Mixture filter, and collect filtrate, vacuum distillation recovered solvent, and add 250g deionized water in residue, precipitate and filter, being dried
After obtain lignin, lignin yield is 22.14%, the pressurized deionized water that is distilled off of filtrate, recyclable ionic liquid.By above-mentioned for 10g system
Standby lignin joins in deionized water, is made into the suspension that mass concentration is 20wt%, regulates suspension PH to 7.5 by NaOH solution, stirs
After mixing 30min, adding 20mmol sodium sulfite in suspension, at 120 DEG C, stirring reaction 8 hours, filter after reaction, obtain filtrate, will
Filtrate carries out concentrated spray and is dried, and prepares sodium lignin sulfonate after drying.
Embodiment 2
A kind of method utilizing agricultural crop straw to prepare sodium lignin sulfonate, comprises the following steps:
Being washed by Caulis et Folium Oryzae, be dried, powder becomes the stalk particle of 3～10mm, then by 20g1-benzyl-3-Methylimidazole. dimethyl phosphate salt, 30g first
Alcohol, 50g corn stalk pellets join in reactor, and at 105 DEG C, heated and stirred is reacted 5 hours, after reaction terminates, by mixing in reactor
Compound filters, and collects filtrate, vacuum distillation recovered solvent, and adds 100g deionized water in residue, precipitates and filters, dried
To going out lignin, lignin yield is 20.13%, the pressurized deionized water that is distilled off of filtrate, recyclable ionic liquid.By above-mentioned for 60g preparation
Lignin joins in deionized water, is made into the suspension that mass concentration is 40wt%, regulates suspension PH to 5.0 with H2SO4 solution, stirs 30min
After, in suspension, add 100mmol sodium sulfite, at 140 DEG C, stirring reaction 6 hours, filter after reaction, obtain filtrate, filtrate entered
Row concentrated spray is dried, and prepares sodium lignin sulfonate after drying.
Claims (4)
1. one kind utilizes the method that agricultural crop straw prepares sodium lignin sulfonate, it is characterised in that comprise the following steps:
The first step: agricultural crop straw is washed, dries, be ground into 3-10mm stalk particle:
Second step: ionic liquid, solvent, agricultural crop straw granule being added in reactor, heated and stirred mixture 1～24 is little under 90～180C
Time, wherein mixture intermediate ion liquid mass fraction is 0.10～0.76；The mass fraction of agricultural crop straw is 0.05～0.34；The quality of solvent is divided
Number is 0.19～0.90；
3rd step: filtered by the mixture in reactor, collects filtrate, removes solvent, recycles；And add in residue and to go in a large number
Ionized water, is settled out lignin, separates and obtains lignin after drying；Continue distillation and remove water, ionic liquid can be reclaimed.The wherein receipts of lignin
Rate is 10.15%～32.19%；The quality of deionized water is 1-10 times of ionic liquid quality；
4th step: lignin obtained above is made into the suspension that mass concentration is 15wt%～40wt%, and regulates the pH value of suspension extremely
4.5～8.5；
5th step: add sodium sulfite in above-mentioned suspension, at 105 DEG C～150 DEG C, stirring reaction 2～10 hours, filter after reaction, are filtered
Liquid.Wherein sodium sulfite is (1.5～4) mmol/g with the ratio of lignin；
6th step: the filtrate of gained is concentrated and is spray-dried, prepares sodium lignin sulfonate.
2. according to claim 1, it is characterised in that described ionic liquid includes 1-butyl-3-Methylimidazole. villaumite, 1-ethyl-3-methylimidazole
Villaumite, 1-pi-allyl-3-Methylimidazole. villaumite, 1-benzyl-3-Methylimidazole. villaumite, 1-hexyl-3-Methylimidazole. villaumite, 1 butyl-3-methyl miaow
Azoles dimethyl phosphate salt, 1-ethyl-3-methylimidazole dimethyl phosphate salt, 1-pi-allyl-3-Methylimidazole. dimethyl phosphate salt, 1-benzyl-3-first
Base imidazoles dimethyl phosphate salt, 1-hexyl-3-Methylimidazole. dimethyl phosphate salt, 1-butyl-3-Methylimidazole. trifluoromethyl sulfonic acid, 1-ethyl-3-
Methylimidazole. trifluoromethyl sulfonic acid, 1-pi-allyl-3-Methylimidazole. trifluoromethyl sulfonic acid, 1-benzyl-3-Methylimidazole. trifluoromethyl sulfonic acid,
1-hexyl-3-Methylimidazole. trifluoromethyl sulfonic acid, 1-butyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazole Methylsulfate,
1-pi-allyl-3-methylimidazolium methylsulfate, 1-benzyl-3-methylimidazolium methylsulfate, 1-hexyl-3-methylimidazolium methylsulfate, 1-
Butyl-3-carboxymethyl imidazoles dimethyl phosphate salt, 1-ethyl-3-carboxymethyl imidazoles dimethyl phosphate salt, 1-benzyl-3-carboxymethyl imidazoles trifluoromethyl
One or more in sulfonate, 1-hexyl-3-carboxymethyl imidazoles trifluoromethyl sulfonic acid.
3. according to claim 1, it is characterised in that described solvent includes the one in water, methanol, ethanol, acetonitrile, glycerol, isopropanol or many
Kind.
4. according to claim 1, it is characterised in that described agricultural crop straw includes corn straw, Caulis et Folium Oryzae, wheat stalk, Caulis Sacchari sinensis straw, Cotton Gossypii
One or more in straw, potato class straw, oil plant straw.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410605746.5A CN105885058A (en) | 2014-11-03 | 2014-11-03 | Method utilizing crop straws to prepare sodium lignosulfonate |
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| CN201410605746.5A CN105885058A (en) | 2014-11-03 | 2014-11-03 | Method utilizing crop straws to prepare sodium lignosulfonate |
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| CN105885058A true CN105885058A (en) | 2016-08-24 |
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ID=56697689
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501571A (en) * | 2017-08-31 | 2017-12-22 | 齐鲁工业大学 | A kind of method that methylimidazole villaumite LiCl DMF systems of 1 butyl 3 prepare fento maize straw |
| CN107501572A (en) * | 2017-08-31 | 2017-12-22 | 齐鲁工业大学 | A kind of method that methylimidazole villaumite LiBr DMF systems of 1 butyl 3 prepare fento maize straw |
| CN111138109A (en) * | 2019-12-26 | 2020-05-12 | 新疆大学 | Cotton stalk lignin-based air entraining agent and preparation method and application thereof |
| CN111138683A (en) * | 2020-01-19 | 2020-05-12 | 茂名市红福化学有限公司 | Sodium lignosulfonate water reducing agent and preparation method thereof |
| CN113562902A (en) * | 2021-08-02 | 2021-10-29 | 海南金海浆纸业有限公司 | Papermaking wastewater treating agent and papermaking wastewater treating method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174754A (en) * | 2011-01-07 | 2011-09-07 | 华南理工大学 | Solvent for separating biomass, and application thereof in selective separation of biomass |
| CN102690423A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院化学研究所有限公司 | Method for producing sodium lignosulphonate by utilizing residues obtained by producing ethanol with crop straws as raw materials |
| CN103408768A (en) * | 2013-08-08 | 2013-11-27 | 中国科学院过程工程研究所 | Method for improving quality of industrial lignin by using ionic liquid |
| CN103408671A (en) * | 2013-08-24 | 2013-11-27 | 中糠有限公司 | Method for preparing carboxymethylcellulose and sodium lignin sulfonate from crop straws |
| WO2014172042A1 (en) * | 2013-03-15 | 2014-10-23 | Sandia Corporation | Synthesis of novel ionic liquids from lignin-derived compounds |
-
2014
- 2014-11-03 CN CN201410605746.5A patent/CN105885058A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174754A (en) * | 2011-01-07 | 2011-09-07 | 华南理工大学 | Solvent for separating biomass, and application thereof in selective separation of biomass |
| CN102690423A (en) * | 2012-06-18 | 2012-09-26 | 河南省科学院化学研究所有限公司 | Method for producing sodium lignosulphonate by utilizing residues obtained by producing ethanol with crop straws as raw materials |
| WO2014172042A1 (en) * | 2013-03-15 | 2014-10-23 | Sandia Corporation | Synthesis of novel ionic liquids from lignin-derived compounds |
| CN103408768A (en) * | 2013-08-08 | 2013-11-27 | 中国科学院过程工程研究所 | Method for improving quality of industrial lignin by using ionic liquid |
| CN103408671A (en) * | 2013-08-24 | 2013-11-27 | 中糠有限公司 | Method for preparing carboxymethylcellulose and sodium lignin sulfonate from crop straws |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501571A (en) * | 2017-08-31 | 2017-12-22 | 齐鲁工业大学 | A kind of method that methylimidazole villaumite LiCl DMF systems of 1 butyl 3 prepare fento maize straw |
| CN107501572A (en) * | 2017-08-31 | 2017-12-22 | 齐鲁工业大学 | A kind of method that methylimidazole villaumite LiBr DMF systems of 1 butyl 3 prepare fento maize straw |
| CN107501572B (en) * | 2017-08-31 | 2019-07-05 | 齐鲁工业大学 | A kind of method that 1- butyl -3- methylimidazole villaumite-LiBr-DMF system prepares fento corn stover |
| CN107501571B (en) * | 2017-08-31 | 2019-07-05 | 齐鲁工业大学 | A kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover |
| CN111138109A (en) * | 2019-12-26 | 2020-05-12 | 新疆大学 | Cotton stalk lignin-based air entraining agent and preparation method and application thereof |
| CN111138683A (en) * | 2020-01-19 | 2020-05-12 | 茂名市红福化学有限公司 | Sodium lignosulfonate water reducing agent and preparation method thereof |
| CN113562902A (en) * | 2021-08-02 | 2021-10-29 | 海南金海浆纸业有限公司 | Papermaking wastewater treating agent and papermaking wastewater treating method thereof |
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Application publication date: 20160824 |