CN106317418B - The method for making sodium lignin sulfonate using corncob acid hydrolysis slag soda boiling black liquor - Google Patents
The method for making sodium lignin sulfonate using corncob acid hydrolysis slag soda boiling black liquor Download PDFInfo
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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
Abstract
The present invention provides the methods for making sodium lignin sulfonate using corncob acid hydrolysis slag soda boiling black liquor.Preparation process includes the following steps：Corncob acid hydrolysis slag soda boiling black liquor is passed through into coarse filtration, then after being concentrated into the concentrated black liquor that solid content is 20% 30% with film, is pumped into reaction kettle, with sulphur acid for adjusting pH to 9 10.5,60 70 DEG C, reacts 0.5 1h.After oxidant and catalyst reaction is added, 40 60 DEG C are cooled to, formaldehyde is added, 80 100 DEG C are warming up to after reaction, sulfonating agent is added, reacts 2 4h.Product is concentrated by triple effect, and solid content is made to reach 30% 40%, is up to state standards up to solid lignin sodium sulfonate, indices using after spray drying.The present invention solves the problems, such as to improve the utility value of corncob acid hydrolysis slag using single to corncob acid hydrolysis slag.
Description
Technical field
The invention belongs to chemical technology field, it is related to a kind of using corncob acid hydrolysis slag soda boiling black liquor being that raw material passes through soda boiling
The method for preparing sodium lignin sulfonate dye dispersant afterwards.
Background technology
The U.S. and China are maximum maize production state in the world, about 2.8 hundred million tons of american corn annual output, the yield in China
It is 1.4 hundred million tons.In maize production, niblet is air-dried per 100t, can obtain the corncob of about 25t, China's corn core raw material
Total amount is very abundant renewable resource in 40,000,000 t or more.
Currently, all conducting a research both at home and abroad around corncob deep processing and comprehensive utilization, a series of corncobs are developed
The ingredient of the approach of comprehensive utilization, corncob is：Content of cellulose 32%--36%, hemi-cellulose content 32%--34%, it is wooden
Cellulose content 17%--20%.In China, the utilization of corncob is still to utilize poly-pentose production D- xyloses, xylitol and Arab
Based on sugar, a large amount of waste will be generated after corncob extracts poly-pentose --- acidolysis slag, main ingredient therein are fibers
Element and lignin, the utilization for this part resource, the common processing method in China are that burning generates steam, this processing side
Formula is that a kind of waste to resource discharges more carbon dioxide into air again simultaneously, leads to the aggravation of greenhouse effects, is not inconsistent
Close China's strategy of sustainable development.
The sodium salt of lignin sulfonic acid is that sodium lignin sulfonate (sodium ligninsulfonate) is a kind of natural height
Molecularly Imprinted Polymer, anionic surfactant.With very strong dispersibility, suitable for solid is dispersed in aqueous medium.By
There is different degrees of dispersibility in the difference of molecular weight and functional group, can be adsorbed on the surface of various solid particles, it can
Carry out metal ion exchanged effect, also because its institutional framework on there are various active groups, thus can generate condensation or with
Hydrogen bond action occurs for other compounds.Industrially, sodium lignin sulfonate is widely used as dispersant and wetting agent.Printing and dyeing industry
Middle dispersant-the NNO used is to be compounded by primary raw material of sodium lignin sulfonate.
Generally there are two types of approach for the production of sodium lignin sulfonate：1) calcium lignosulfonate is passed through into ion exchange；2) it is making
During slurry, with sodium carbonate or sodium hydroxide, replace calcium oxide or calcium hydroxide.This method is more rare, because
The price of sodium carbonate sodium hydroxide is usually above calcium oxide or calcium hydroxide.
It is that raw material prepares sodium lignin sulfonate with the spent pulping liquor in paper mill, general there are three types of preparation methods.1. sulfurous acid
Sulphite or disulfate contained in the spent pulping liquor of hydrogen calcium pulp-making method directly with the hydroxy combining in lignin molecule
Generate lignosulfonates.10% milk of lime is added into waste liquid, 30min is heated at (95 ± 2) DEG C.Calcifying solution is stood
Sedimentation, sediment filter out, washing after vulcanization acid.Filtering removes calcium sulfate.Then Na is added into filtrate2CO3, make sulfomethylated lignin
Sour calcium changes into sodium sulfonate, after reaction, stands, is filtered to remove the impurity such as calcium sulfate.Filtrate concentrates, and crystallisation by cooling obtains product.2. with
Papermaking wastewater obtained by lye slurrying is raw material.The concentrated sulfuric acid 50% or so is added first into waste liquid, milk of lime is used after reaction, through heavy
Drop filters, and mashing, acid is molten, and sodium carbonate is added to convert, and concentrates, dry product.3. waste liquid is raw material obtained by careless class pulp-making method.
Method is the same as 2.
Currently, the production technology of sodium lignin sulfonate as previously mentioned, substantially there are three types of different principle preparation method, but this
A little methods are complex on the whole, and gained sodium lignin sulfonate purity is very low, domestic production, purification technique still need into
One step is improved, although also, these reaction principles have been well known, particular technique details therein, however it remains
Many many restrictions sexual factors for being difficult to capture, hinder product quality, yield and cost control.Although China is currently on the market
There are the U.S., Europe, South Korea, Japan, or even the sodium lignin sulfonate product of Russia and imported from South Africa, but it is respectively deposited
In corresponding disadvantage, for example originating from the sodium lignin sulfonate product in the U.S., although purity, quality are preferable, preparation method is deposited
It is with high costs in relatively big difference, substantially increase the production cost of enterprise.
Invention content
The purpose of the present invention is to provide a kind of making wooden sodium sulfonates at low cost, easy to operate, environmentally friendly
Method.
The present invention provides a kind of methods making sodium lignin sulfonate using corncob acid hydrolysis slag soda boiling black liquor, including with
Lower step：
(1) coarse filtration：Coarse filtration is carried out to corncob acid hydrolysis slag soda boiling black liquor with filter；
(2) film concentrates：The black liquor after coarse filtration is concentrated with ultrafiltration membrane, its solid content is made to reach 20%-
30%；
(3) through peroxidization, lignin molecule key is made to be broken；
(4) pass through sulfonating reaction, obtain the sodium lignin sulfonate of low concentration；
(5) it concentrates, be spray-dried：Black liquor after sulfonation makes solid content reach 30%-40%, then pass through by concentration
It crosses after spray drying up to solid powder.
Wherein, the raw material black liquor is to extract the waste acidolysis slag that generates after poly-pentose using corncob, mainly at
It is divided into cellulose and lignin, is carried out obtained black liquor after soda boiling, centrifugation.The corncob acid hydrolysis slag soda boiling of step (1)
In black liquor, solid content 9%-12%, density 1.03-1.04g/ml, pH value 10.5-12, the content of hemicellulose
0.15%-0.2%, content of lignin 3%-4%, lignin account for the ratio 30%-35% of solid content.
Aperture≤10 μm of the used filter of black liquor coarse filtration in step (1).
Traditional coarse filtration is usually only capable of removing the larger cellulose etc. of large particulate matter and part, and of the invention is thick
Aperture≤10 μm of filtering preferably used filter, can effectively remove smaller dust and cellulose.For removing fiber
Element and dust are most preferably 3-6 μm, and most preferably 3 μm, aperture is excessive, easily leads to impurity and is interfered in late phase reaction, and aperture is too small,
Then filter effect is poor, takes and increases, and cost is higher.
Ultrafiltration membrane uses the alkaline-resisting film of 1000MD-3000MD in step (2).
Black liquor after coarse filtration is concentrated with 1000-3000MD, 40-50 DEG C of temperature, pressure 1.0-1.5MPa makes it
Solid content reaches 20%-30%.Black liquor solid content is 20-25% after concentration, and lignin purity is in 55-65%.
Preferably, inorganic salts therein, colloid and low molecular weight are removed to black liquor processing with the film of 3000MD molecular weight
Organic matter is carried out at the same time concentration.
In step (3) oxidation reaction：Black liquor pH value 9-10.5 is adjusted before oxidation, and is added into black liquor and is contained with solid content
Amount calculates the ferrous sulfate of the hydrogen peroxide and 0.15%-0.2% of 1%-3%, and heating carries out oxidation reaction.
The oxidation reaction concrete operations of step (3) are to adjust black liquor pH value to 8-11,65 DEG C of -75 DEG C of reactions with sulfuric acid
0.25h-0.75h, after 1%-3% hydrogen peroxide and 0.05-0.2% ferrous sulfate is added, 65 DEG C of -75 DEG C of reaction 0.5-3h make
Lignin molecule key is broken.
Preferably, in step of the invention (3) oxidation reaction：Black liquor pH value is adjusted with 20% sulfuric acid to 9-10.5,70
DEG C reaction 0.5h, is added 1-3% hydrogen peroxide and 0.05-0.2% ferrous sulfate (with black liquor solid content meter), 70 DEG C of reactions
1-2h, preferably 1h make lignin molecule key be broken.
Through peroxidating, make lignin structure unit phenyl ring and side chain size degradation, makes lignin easy sulfonation at low ambient temperatures.This
The important feature of invention i.e. be that pre-oxidation step is arranged before sulfonation, this for low-temperature sulfonation technique it is smooth, efficiently into
The performance of row and final products has great influence.
In step (4) sulfonating reaction：Black liquor after oxidation is cooled to 45-50 DEG C, is added with black liquor solid content meter
9%-15% formaldehyde reacts 1-2h, lignin molecule is made to be condensed；It is warming up to 80-100 DEG C, is added with black liquor solid content meter
0.5%-1% sodium sulfites, sulfonation 2-4h.
Sulfonating reaction is the sulfonating reaction of the prior art where core of the invention, generally all at 60 DEG C or more, invention
People has found under study for action, although this high temperature sulfonation can relatively efficiently control the Direction of Reaction, whole condensation degree is difficult to pre-
It surveys, sulfonation process is more difficult to control, and the molecule space distribution of polymer may be uneven, causes the physicochemical property of final products poor；
Inventor had found at a lower temperature by many experiments, i.e., 50 DEG C or less are reacted that (not pretreated lignin exists
More difficult generation of sulfonating reaction or sulfonation are incomplete under the conditions of this), the specific progress of sulfonating reaction can be preferably controlled, is made pre-
Phase product is carried out to the direction of polymerization with desirable molecular weight, molecular distribution, to obtain the product with excellent specific property.
The additive amount of formaldehyde and reaction influence the condensation degree of lignin, and the condensation degree of lignin influences the dispersion force of product
And thermal stability, because lignin molecule is bigger, its adsorption capacity on dyestuff discrete particles is stronger, at relatively high temperatures,
It is not easy to desorb from particle surface.
In step (5), the black liquor solid content after sulfonation is 20%-25%, is concentrated through triple effect, solid content is made to reach
Dry to 30%-40%, obtained sodium lignin sulfonate product moisture content is not more than 8%.
The method of the present invention, by organically introducing pre-oxidation step before sulfonation procedure, to lignin molecule
It is pre-processed, makes its molecular scission, to effectively reduce the temperature of sulfonation, and improve the uniformity of sulfonation, sulfonation
Efficiency, obtained structure uniformly, the sodium lignin sulfonate with physical and chemical indexes such as excellent dispersibility, thermal stability, Ke Yiguang
It is general to be used as dye dispersant；Also, the method for the present invention has given up the complexity in the high-grade sodium lignin sulfonate production of high-purity
Cumbersome purification step has produced the sodium lignin sulfonate of high quality using simple method, reduces production cost, significantly
Product quality is improved, and the raw material of the present invention is environmentally harmful waste, method of the invention effectively eliminates ring
Border is polluted, and is turned waste into wealth, and is had a good application prospect, economic benefit and social benefit.In turn, the present invention also provides according to
The preparation-obtained sodium lignin sulfonate of the above method and the sodium lignin sulfonate are used as the purposes of dye dispersant.
Lignin and cellulose are detached corncob acid hydrolysis slag by soda boiling, centrifugation by the present invention, the filtering of lignin process,
Film process, oxidation sulfonating reaction, concentration, the dry dye dispersant made.Cellulose can be alcohol, citric acid by microbe conversion
With the products such as lactic acid.While solving atmosphere pollution, and the utility value of corncob is improved, has obtained good lignin
Sodium sulfonate product, product have excellent physicochemical property, may replace the wooden of expensive imported product to be produced with low cost
Plain sodium sulfonate, simplifies technological process, controls production cost, realizes waste utilization, is conducive to energy conservation and environmental protection.
Specific implementation mode
The content that following embodiment further illustrates the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case of spirit of that invention and essence, to modifications or substitutions made by the method for the present invention, step or condition, the present invention is belonged to
Range.
Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Black liquor described in embodiment is to extract the waste acidolysis slag generated after poly-pentose using corncob, and main component is
Cellulose and lignin are carried out obtained black liquor after soda boiling, centrifugation.In corncob acid hydrolysis slag soda boiling black liquor, solid content
Content is 9%-12%, density 1.03-1.04g/ml, pH value 10.5-12, the content 0.15%-0.2% of hemicellulose, wooden
Cellulose content 3%-4%, lignin account for the ratio 30%-35% of solid content.
Embodiment 1
1. raw material and formula：
Black liquor:78.2kg
Hydrogen peroxide：0.118kg
Ferrous sulfate：0.005kg
Formaldehyde：0.197kg
Sodium sulfite：0.079kg
2. processing step and technological parameter：
It is that 5-10 μm of coarse filter carries out coarse filtration to black liquor with aperture, weight is 78.2kg, solid content after filtering
It is 9.88%, content of lignin 3.1% uses molecular weight cut off for 1000D ultrafiltration membrane treatments, processing time 6.42h, fortune
Row pressure 1.5MPa, 40 DEG C of running temperature, black liquor weight is 15kg after processing, and wherein solid content is 21.79%, lignin
It is 13.11%.Take black liquor after 3kg film process to carry out sulfonation experiment, with 20% sulfuric acid adjust black liquor pH value to 10.1,70 DEG C it is anti-
0.5h is answered, 118g hydrogen peroxide and 5g ferrous sulfate is added, 70 DEG C of reaction 1h are cooled to 45 DEG C of addition formaldehyde 197g, react 2h,
Then 79g sodium sulfites are added, are warming up to 95 DEG C, react 4h.Temperature fall after reaction.Product is brown liquid, is led to
Sodium lignin sulfonate after crossing triple effect concentration and being spray-dried.
Embodiment 2
1. raw material and formula：
Black liquor:90.33kg
Hydrogen peroxide：0.125kg
Ferrous sulfate：0.005kg
Formaldehyde：0.208kg
Sodium sulfite：0.083kg
2. processing step and technological parameter：
Coarse filtration is carried out to black liquor with coarse filter, weight is 90.33kg, solid content 10.19%, wood after filtering
Lignin content is 3.24%, uses molecular weight cut off for 3000D ultrafiltration membrane treatments, processing time 8.1h, inlet pressure
1.2MPa, temperature 50 C, black liquor weight is 16.34kg after processing, and wherein solid content is 22.78%, and lignin is
13.87%.Black liquor carries out sulfonation experiment after taking 3kg film process, and black liquor pH value is adjusted to 9.96,70 DEG C of reactions with 20% sulfuric acid
125g hydrogen peroxide and 5g ferrous sulfate is added in 0.5h, and 70 DEG C of reaction 1h, then 45 DEG C of addition formaldehyde 208g, reaction 2h are added
83g sodium sulfites are warming up to 95 DEG C, react 4h.Temperature fall after reaction.Product is brown liquid, dense by triple effect
Up to sodium lignin sulfonate after contracting and spray drying.
Embodiment 3
1. raw material and formula：
Black liquor:89.75kg
Hydrogen peroxide：0.138kg
Ferrous sulfate：0.006kg
Formaldehyde：0.230kg
Sodium sulfite：0.092kg
2. processing step and technological parameter：
Coarse filtration is carried out to black liquor with coarse filter, weight is 89.75kg, solid content 10.33%, wood after filtering
Lignin content is 3.23%, uses molecular weight cut off for 3000D ultrafiltration membrane treatments, processing time 8.5h, operating pressure
1.0MPa, temperature 45 C, black liquor weight is 14.38kg after processing, and wherein solid content is 25.31%, and lignin is
15.31%.Black liquor carries out sulfonation experiment after taking 3kg film process, and black liquor pH value is adjusted to 9.89,70 DEG C of reactions with 20% sulfuric acid
138g hydrogen peroxide and 6g ferrous sulfate is added in 0.5h, and 70 DEG C of reaction 1h, then 45 DEG C of addition formaldehyde 230g, reaction 2h are added
92g sodium sulfites are warming up to 95 DEG C, react 4h.Temperature fall after reaction.Product is brown liquid, dense by triple effect
Up to sodium lignin sulfonate after contracting and spray drying.
Embodiment 4
1. raw material and formula：
Black liquor:80.06kg
Hydrogen peroxide：0.113kg
Ferrous sulfate：0.0045kg
Formaldehyde：0.190kg
Sodium sulfite：0.076kg
2. processing step and technological parameter：
Coarse filtration is carried out to black liquor with coarse filter, weight is 87.5kg after filtering, and solid content 9.97% is wooden
Cellulose content is 3.09%, uses molecular weight cut off for 1500D ultrafiltration membrane treatments, processing time 7.3h, operating pressure 1.5MPa,
Temperature 50 C, black liquor weight is 15.01kg after processing, and wherein solid content is 20.94%, lignin 12.6%.Take 3kg
Black liquor carries out sulfonation experiment after film process, adjusts black liquor pH value to 9.95,70 DEG C of reaction 0.5h with 20% sulfuric acid, 113g is added
Hydrogen peroxide and 4.5g ferrous sulfate, 70 DEG C of reactions 1h, 45 DEG C of addition formaldehyde 190g react 2h, then addition 76g sulfurous acid
Sodium is warming up to 95 DEG C, reacts 4h.Temperature fall after reaction.Product is brown liquid, is concentrated and is sprayed by triple effect and is dry
Up to sodium lignin sulfonate after dry.
Embodiment 5
Currently, China's major part sodium lignin sulfonate is low-end product, national requirements lignin sulfonic acid sodium content is between 45-
50%, calcium-magnesium content：1% or less is qualified products.
In the present embodiment, embodiment 1-4 products obtained therefroms are detected, it is found that the product purity of the present invention is significantly larger than state
Family's standard.Specifically, after testing, the purity of sodium lignin sulfonate is not less than 86%, calcium-magnesium content：0.2% hereinafter, lignin
Sodium sulfonate molecular structure is more uniform, monomer structure is smaller, but bulk polymerization degree is higher.Through application, the embodiment of the present invention is found
After sodium lignin sulfonate prepared by 1-4 is applied as dye dispersant, there is excellent adsorptivity, heat-resistant stable.
Following table is the numerical value of the part Testing index of the sodium lignin sulfonate dye dispersant obtained by above four batches of embodiments
Quantitative display be shown in Table 1：
The Testing index of 1 sodium lignin sulfonate dye dispersant of table
| Serial number | Detection project | Testing result |
| 1 | Moisture content | ≤ 8.0% |
| 2 | PH value | 8.0-10.0 |
| 3 | Inorganic salts | ≤ 2.0% |
| 4 | Dispersion force (with standard items ratio) | ≥100 |
| 5 | Reduced sugar | ≤ 3.0% |
| 6 | Water-insoluble | ≤ 0.1% |
| 7 | The total content of magnesium and calcium | ≤ 0.2% |
| 8 | Heat-resistant stability grade (DEG C) | ≥4-5(130℃) |
Other quantitative, qualitative indexes reach and exceed ZBG52001 standards.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (7)
1. a kind of method making sodium lignin sulfonate using corncob acid hydrolysis slag soda boiling black liquor, it is characterised in that：Include successively
Following steps：
(1) coarse filtration：Coarse filtration is carried out to corncob acid hydrolysis slag soda boiling black liquor；
(2) film concentrates：The black liquor after coarse filtration is concentrated with ultrafiltration membrane, its solid content is made to reach 20%-30%；
(3) through peroxidization, lignin molecule key is made to be broken, in the oxidation reaction：Black liquor pH value 9- is adjusted before oxidation
10.5, and the ferrous sulfate of hydrogen peroxide and 0.15%-0.2% that 1%-3% is calculated with solid content is added into black liquor,
Heating carries out oxidation reaction；
(4) pass through sulfonating reaction, obtain the sodium lignin sulfonate of low concentration, in the sulfonating reaction：By the black liquor drop after oxidation
Temperature is added with black liquor solid content meter 9%-15% formaldehyde to 45-50 DEG C, reacts 1-2h, lignin molecule is made to be condensed；Heating
To 80-100 DEG C, it is added with black liquor solid content meter 0.5%-1% sodium sulfites, sulfonation 2-4h；
(5) it concentrates, be spray-dried：Black liquor after sulfonation makes solid content reach 30%-40%, using spray by concentration
Up to solid powder after mist drying.
2. preparation method according to claim 1, which is characterized in that in the corncob acid hydrolysis slag soda boiling black liquor of step (1),
Solid content is 9%-12%, density 1.03-1.04g/ml, the content 0.15%-0.2% of hemicellulose, content of lignin
3%-4%, lignin account for the ratio 30%-35% of solid content.
3. preparation method according to claim 1, which is characterized in that the used filter of black liquor coarse filtration in step (1)
Aperture≤10 μm.
4. preparation method according to claim 1, which is characterized in that ultrafiltration membrane uses 1000MD-3000MD in step (2)
Alkaline-resisting film.
5. preparation method according to claim 1, which is characterized in that the oxidation reaction concrete operations of step (3) are oxidation
After adjusting black liquor pH value with sulfuric acid before, 65 DEG C of -75 DEG C of reaction 0.25h-0.75h, after hydrogen peroxide and ferrous sulfate is added, 65
DEG C of -75 DEG C reaction 0.5-3h, make lignin molecule key be broken.
6. preparation method according to claim 1, it is characterised in that：In step (5), the black liquor solid content after sulfonation
It for 20%-25%, is concentrated through triple effect, solid content is made to reach 30%-40%, dry, obtained sodium lignin sulfonate product
Moisture content is not more than 8%.
7. any preparation-obtained sodium lignin sulfonates of preparation method of claim 1-6.
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| CN110615896B (en) * | 2019-09-04 | 2021-12-03 | 上海昶法新材料有限公司 | Method for preparing lignosulfonate water reducing agent from dissolving pulp pulping waste liquid |
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