CN107474259A - A kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk - Google Patents
A kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk Download PDFInfo
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- CN107474259A CN107474259A CN201610401189.4A CN201610401189A CN107474259A CN 107474259 A CN107474259 A CN 107474259A CN 201610401189 A CN201610401189 A CN 201610401189A CN 107474259 A CN107474259 A CN 107474259A
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- lignin sulfonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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Abstract
The invention discloses a kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk discarded object.Filtered after cotton stalk powder is completely dissolved, the pH value for adjusting filtrate make it that precipitation is complete, and then heating and thermal insulation for a period of time, is filtered and washed to neutrality and obtain crude product lignin.Crude product lignin is dissolved again, adds anhydrous sodium sulfite and ferric trichloride, adjusts the pH value of solution, agitating and heating carries out sulfonating reaction, sodium lignin sulfonate is obtained after filtering（Crude product）.This method makes full use of that waste resource, technique are simple, cost is cheap, reaction temperature is gentle, and the sodium lignin sulfonate with applications well prospect antioxygenic property is prepared.
Description
Technical field
The present invention relates to antioxidant technology field, is a kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk as raw material.
Background technology
Free radical is molecule or ion with unpaired electron, is the product of organism metabolism.Certain density free radical is one of necessary condition that body carries out normal activities, the physiological action of uniqueness can be shown, the redox reaction of many metabolic processes of body may result from by base, but excessive free radical is then harmful to body, it can cause body injury to be denatured, cause the diseases such as aging, tumour, cancer and heart disease, produce physiological and pathological change, relatively common free radical has O2-HOROORONO
The present invention relates to antioxidant technology field, is a kind of method that antioxidant sodium lignin sulfonate is prepared using cotton stalk as raw material.
In view of the importance of free radical, the work for finding efficient, cheap, less toxic or even nontoxic antioxidant receives much concern.Most of antioxidant commonly used at present in domestic food is all synthesis, such as commercial antioxidants butylated hydroxy anisole（BHA）, 2,6- di-tert-butyl-4-methy phenols etc., although with stronger inoxidizability, there is various potential side effect and the toxic effect of enzyme system to human body, therefore, natural, efficient, less toxic antioxidant is found from plant turns into an inexorable trend of antioxidant research and development.
Research is found, under certain condition, sodium lignin sulfonate has the bioactivity such as preferable radicals scavenging and oxidation resistance, anticancer change, anti-mutagenesis and some animal vivo protein utilization rates of raising, autoxidation and the depolymerization of cellulose can be suppressed, therefore with the potentiality for being widely used in food, cosmetic industry and medical industry.Therefore, it is particularly important to study life of new, safe and stable, the natural antioxidants to people.
Cotton stalk is mainly made up of cellulose, hemicellulose and lignin, and wherein lignin about accounts for 25%.As Chan Mian states the biggest in the world, annual about 30,000,000 tons of the by-product cotton stalk of China, however, present situation be most of cotton stalk all with chopping and returning, burn or the plain mode such as discarded is handled, do not carry out recycling.The yield of cotton stalk is 4-6 times of cotton, the resources such as substantial amounts of water, fertilizer, soil, heat are expended in its forming process, and China's resource scarcity per capita, Xinjiang is located in arid area, face the objective limitation of structural water shortage and ecological environment frailty, cotton stalk should avoid the wasting of resources and problem of environmental pollution that simple process is brought by efficient high added value trans-utilization on the spot.Therefore, to be come out from cotton stalk by lignin separation and sodium lignin sulfonate is prepared, as a kind of natural antioxidant, there will be highly important application value.
Some production methods that sodium lignin sulfonate is prepared using agricultural crop straw are reported by open source literature in recent years, we find following some Chinese patents：
1. the A of patent No. CN 102690423 report the method that sodium lignin sulfonate is produced using the residue of preparing alcohol from stress or stalk of agricultural crops as raw material, it is mainly characterized by：By the residue of preparing alcohol from stress or stalk of agricultural crops（Moisture content 90%）Filtration, purification is carried out, is then concentrated by evaporation through evaporation concentration device, hydrogenation sodium oxide molybdena adjusts pH value, adds sodium sulfite, is reacted under certain temperature, spray drying obtains sodium lignin sulfonate product afterwards, and is used as cement water reducing agent.
2. the A of patent No. CN 102140173 report a kind of method that sodium lignin sulfonate is produced using sodium sulfite reed black liquor of pulp making.Reed is used into alkaline sodium sulfite method boiling, sulfite ion SO32- and OH- are included in cooking liquor, controls pH10, obtains required sodium sulfite reed black liquor of pulp making.The extraction of sodium sulfite reed black liquor of pulp making, evaporation and concentration, spray drying are obtained into sodium lignin sulfonate again.
3. the patent No. 200910036955.1 discloses one kind using Wheat Straw Lignin from Alkali Pulping as primary raw material, the method for preparing highly sulfonated sodium lignosulfonate.Wheat Straw Lignin from Alkali Pulping is subjected to free radical cracking reaction under normal pressure, 65 ~ 75 DEG C of condition of water bath heating, then aldehydes are added dropwise, reacted 10 ~ 20 minutes under the conditions of microwave radiation, add and contain 20 ~ 50 parts by weight sulfonating agent aqueous solution, reacted 1.0 ~ 2.5 hours under the conditions of 300 ~ 1200W microwave powers, be prepared for a kind of sodium lignin sulfonate having compared with highly sulfonated.
The advantages of above-mentioned patent is reported is the twice laid of raw material, but the evaporation, concentration, microwave radiation and sulfonation modifying technique in method are consumed energy, are time-consuming, and sodium lignin sulfonate production cost is higher.
The content of the invention
It is an object of the invention to provide one kind using agricultural wastes --- the method that cotton stalk prepares antioxidant sodium lignin sulfonate as raw material.With it is other by raw material or black liquor of pulp making and papermaking wastewater of agricultural waste material be compared with raw material prepares the method for sodium sulfonate, this method technique is simple, and cost is cheap, and prepared sodium sulfonate can meet the requirement of antioxidant.
To reach above-mentioned purpose, the technical solution adopted for the present invention to solve the technical problems is：
1. the preparation of crude product lignin：20 g cotton stalk powder are weighed in beaker, add hot water by DDGS preliminarily solubilised, the mL 5% ~ 30% of 5 mL ~ 40 alkaline solution is added, heats 12 ~ 36 h at 50 DEG C ~ 100 DEG C, make the lignin dissolution in cotton stalk powder, filter.Adjust the pH of filtrate so that lignin deposit is complete, the min of heating and thermal insulation 20 ~ 100 at 50 ~ 100 DEG C, filters, and washs to neutrality, and precipitation is dried, obtains crude product lignin.
2. the preparation of sodium lignin sulfonate：Crude product lignin is put into suitable quantity of water, the alkaline solution for adding the mL 5% ~ 30% of 1 mL ~ 10 is allowed to dissolve, and adds 5 ~ 15 g anhydrous sodium sulfites and 0.05 ~ 5 g ferric trichloride, and the pH of solution is adjusted with dilute sulfuric acid, control reaction volume is less than 100 ~ 200 mL, solution is gone in 250 mL three-neck flasks, stirring is warming up to 50 ~ 150 DEG C, sulfonating reaction 2 ~ 8 hours, cooling, stand, filtering, filtrate drying be can obtain into sodium lignin sulfonate（Crude product）.
Brief description of the drawings
Fig. 1 lignin, sodium lignin sulfonate（Crude product）And sodium lignin sulfonate（Finished product）Infrared spectrum
Fig. 2 sodium lignin sulfonates（Crude product, finished product）, Vc is to Fe3+ reducing power
Fig. 3 sodium lignin sulfonates（Crude product, finished product）, Vc and composite antioxidant be to the measure of oil peroxidation value
Fig. 4 sodium lignin sulfonates（Crude product, finished product）, Vc is to the clearance rate of nitrite ion
Fig. 5 sodium lignin sulfonates（Crude product, finished product）, Vc is to the clearance rate of hydroxyl radical free radical
Fig. 6 sodium lignin sulfonates（Crude product, finished product）, Vc is to the clearance rate of ultra-oxygen anion free radical
Fig. 7 VC and sodium lignin sulfonate（Crude product, finished product）To DPPH
Fig. 8 sodium lignin sulfonates（Crude product）OH, O2, DPPHNO2- elimination effect are compared.
Embodiment
Embodiment 1, cotton stalk obtain as follows for the sodium lignin sulfonate of raw material：The first step, 20 g cotton stalk powder are weighed in beaker, add hot water by DDGS preliminarily solubilised, add the mL 5% ~ 30% of 5 mL ~ 40 alkaline solution, heat 12 ~ 36 h at 50 DEG C ~ 100 DEG C, make the lignin dissolution in cotton stalk powder, filter；Second step, adjust the pH of filtrate so that precipitation is complete, the min of heating and thermal insulation 20 ~ 100 at 50 ~ 100 DEG C, filters, and washs to neutrality, and precipitation is dried, obtains crude product lignin；3rd step, crude product lignin is put into suitable quantity of water, the alkaline solution for adding the mL 5% ~ 30% of 1 mL ~ 10 is allowed to dissolve, add 5 ~ 15 g anhydrous sodium sulfites and 0.05 ~ 5 g ferric trichloride, pH is adjusted with dilute sulfuric acid, control reaction volume is less than 100 ~ 200 mL, solution is gone in 250 mL three-neck flasks, stirring is warming up to 50 ~ 150 DEG C, sulfonating reaction 2 ~ 8 hours, cool down, stand, filtering, filtrate drying be can obtain into sodium lignin sulfonate（Crude product）.
Embodiment 2, cotton stalk obtain as follows for the sodium lignin sulfonate of raw material：20 g cotton stalk powder are weighed in beaker, add hot water by DDGS preliminarily solubilised, 5 mL or 40 mL 5% or 30% NaOH solution is added, heats 12 h or 36 h at 50 DEG C or 100 DEG C, make the lignin dissolution in cotton stalk powder, filter.With the pH of sulfuric acid regulation filtrate so that precipitation is complete, the min of heating and thermal insulation 20 or 100 min at 50 DEG C or 100 DEG C, filters, and washs to neutrality, and precipitation is dried, obtains crude product lignin.Crude product lignin is put into suitable quantity of water, the NaOH solution for adding 1 mL or 10 mL 5% or 30% is allowed to dissolve, and adds 5 g or 15 g anhydrous sodium sulfites and 0.05 g or 5 g ferric trichloride, and pH is adjusted with dilute sulfuric acid, control reaction volume is less than 100 ~ 200 mL, solution is gone in 250 mL three-neck flasks, stirring is warming up to 50 DEG C or 150 DEG C, the h of sulfonating reaction 2 or 8 h, cooling, stand, filtering, filtrate drying be can obtain into sodium lignin sulfonate（Crude product）.
Embodiment 3, as the optimization of above-described embodiment, the alkaline solution of embodiment 3 is sodium hydroxide or potassium hydroxide or ammoniacal liquor.
Embodiment 4, it is with the difference of above-described embodiment, make it that precipitation is complete with the pH of sulfuric acid or hydrochloric acid or nitre acid-conditioning solution in the second step of embodiment 4.
Embodiment 5, as the optimization of above-described embodiment, crude product lignin is put into suitable quantity of water in the 3rd step of embodiment 5, the sodium hydroxide or potassium hydroxide or ammonia spirit for adding the mL 5% ~ 30% of 1 mL ~ 10 are allowed to dissolve.
Embodiment 6, as the optimization of above-described embodiment, pH to 8 ~ 12 is adjusted with dilute sulfuric acid in the 3rd step in embodiment 6.
, can be according to above having a talk about bright modifications and variations correlated condition it should be appreciated that for those of ordinary skills, and all these modifications and variations should all belong to the protection domain of claim belonging to the present invention.
The sodium lignin sulfonate obtained below to above-described embodiment（Crude product）With ascorbic acid（Vc）And sodium lignin sulfonate（Finished product）Compared in terms of inoxidizability and Scavenging ability, comparing result is as follows：
Fig. 1 is lignin, sodium lignin sulfonate（Crude product）And sodium lignin sulfonate（Finished product）Infrared spectrogram, 1100 cm-1 or so be sulfonic vibration absorption peak.Fig. 2 is sodium lignin sulfonate（Crude product, finished product）, Vc is to Fe3+ reducing power, sodium lignin sulfonate（Crude product）Oxidation resistance it is weaker than vitamin C, but compare sodium lignin sulfonate（Finished product）Oxidation resistance it is strong.Fig. 3 is sodium lignin sulfonate（Crude product, finished product）, Vc and composite antioxidant be to the measure of oil peroxidation value, sodium lignin sulfonate（Crude product）Sodium lignin sulfonate is better than to the inoxidizability of grease（Finished product）And Vc, and the effect of composite antioxidant is best.Fig. 4 is sodium lignin sulfonate（Crude product, finished product）, Vc is to the clearance rate of nitrite ion, sodium lignin sulfonate（Crude product）Sodium lignin sulfonate is substantially compared to the clearance rate of nitrite anions（Finished product）The clearance rate of nitrite ion is higher by a lot, also above the clearance rate of Vc solution；Fig. 5 is sodium lignin sulfonate（Crude product, finished product）, Vc is to the clearance rate of hydroxyl radical free radical, sodium lignin sulfonate（Crude product）Sodium lignin sulfonate is better than to the elimination effect of hydroxyl radical free radical（Finished product）, maximum material removal rate can reach 48% or so；Fig. 6 is sodium lignin sulfonate（Crude product, finished product）, Vc to the clearance rate of ultra-oxygen anion free radical, when the concentration of sodium lignin sulfonate is not less than 0.8 mg/mL, sodium lignin sulfonate（Crude product）Concentration increases more obvious to the elimination effect of superoxide radical.In addition, Vc is best to the elimination effect of ultra-oxygen anion free radical, sodium lignin sulfonate（Crude product）Effect is taken second place.Fig. 7 is VC and sodium lignin sulfonate（Crude product, finished product）It is sodium lignin sulfonate to DPPHDPPH8 to DPPHVc（Crude product）OH, O2, DPPHNO2- elimination effect are compared, sodium lignin sulfonate（Crude product）To OH, O2-, DPPHVc, but for relative sodium lignin sulfonate finished product, its elimination effect is preferable.As seen from the figure, sodium lignin sulfonate（Crude product）It is preferable to NO2- elimination effects, O2- elimination effect is taken second place.
In summary, prepared sodium lignin sulfonate is to hydroxyl radical free radical（•OH）, superoxide anion（O2−•）Free radical, DPPH.free radical（DPPH•）And nitrite anions（NO2-•）It is respectively provided with preferable Scavenging activity.Foundation is provided for the functional food of rational exploitation and utilization sodium lignin sulfonate resource and development of new, medicine, medical treatment, rubber and cosmetics.
Claims (5)
- A kind of 1. method that antioxidant sodium lignin sulfonate is prepared using cotton stalk discarded object, it is characterised in that be prepared according to the following steps obtaining：20 g cotton stalks powder with hot water are subjected to preliminarily solubilised, add the mL 5% of 10 mL ~ 40 ~ 30% alkaline solution, 12 ~ 36 h are heated at 50 DEG C ~ 100 DEG C, make the lignin dissolution in cotton stalk powder, filtered； Adjust the pH of filtrate so that precipitation is complete, the min of heating and thermal insulation 20 ~ 100 at 50 ~ 100 DEG C, filters, and washs to neutrality, and precipitation is dried, obtains crude product lignin；Crude product lignin is put into suitable quantity of water, adds the mL 5% of 1 mL ~ 15 ~ 30% alkaline solution is allowed to dissolve, and adds 5 ~ 15 G anhydrous sodium sulfites and 0.05 ~ 5 G ferric trichloride, pH is adjusted with dilute sulfuric acid, control reaction volume is less than 100 ~ 200 mL, and stirring is warming up to 50 ~ 150 DEG C, sulfonating reaction 2 ~ 8 hours, cooled down, stands, filtering, and filtrate drying can obtain into sodium lignin sulfonate（Crude product）.
- 2. antioxidant sodium lignin sulfonate according to claim 1, it is characterised in that alkaline solution is sodium hydroxide or potassium hydroxide or ammoniacal liquor.
- 3. according to the antioxidant sodium lignin sulfonate described in claim 1 or 2, it is characterised in that make it that precipitation is complete with the pH of sulfuric acid or hydrochloric acid or nitre acid-conditioning solution.
- 4. according to the antioxidant sodium lignin sulfonate described in claim 1 or 2 or 3, it is characterised in that crude product lignin is put into suitable quantity of water, adds the mL 5% of 1 mL ~ 15 ~ 30% sodium hydroxide or potassium hydroxide or ammonia spirit is allowed to dissolve.
- 5. according to the antioxidant sodium lignin sulfonate described in claim 1 or 2 or 3 or 4, it is characterised in that adjust pH to 8 ~ 12 with dilute sulfuric acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503859A (en) * | 2018-12-06 | 2019-03-22 | 齐鲁工业大学 | A method of highly sulfonated sodium lignosulfonate is prepared using wheat stalk |
| CN109986676A (en) * | 2019-04-06 | 2019-07-09 | 安徽凯彦达环保餐具有限公司 | A kind of production technology for the disposable lunch-box that can be degraded in a natural environment |
| 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 |
-
2016
- 2016-06-08 CN CN201610401189.4A patent/CN107474259A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503859A (en) * | 2018-12-06 | 2019-03-22 | 齐鲁工业大学 | A method of highly sulfonated sodium lignosulfonate is prepared using wheat stalk |
| CN109986676A (en) * | 2019-04-06 | 2019-07-09 | 安徽凯彦达环保餐具有限公司 | A kind of production technology for the disposable lunch-box that can be degraded in a natural environment |
| 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 |
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