CN109777353A - A kind of clay grinding aid and preparation method thereof - Google Patents
A kind of clay grinding aid and preparation method thereof Download PDFInfo
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- CN109777353A CN109777353A CN201910219480.3A CN201910219480A CN109777353A CN 109777353 A CN109777353 A CN 109777353A CN 201910219480 A CN201910219480 A CN 201910219480A CN 109777353 A CN109777353 A CN 109777353A
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Abstract
The invention discloses a kind of clay grinding aids and preparation method thereof, comprising steps of alkali lignin purifies, by alkali lignin with 1, after the mixed solvent dissolution that 4- dioxane and water are prepared, it is stood after being vigorously stirred after adjusting pH to 5.0~5.5, centrifuge separation, the alkali lignin purified after obtained solid sample is vacuum dried；Microbial fermentation, by purified alkali lignin heap in fermentation tank and turn over it is even, turn over it is even during successively culture solution, Phanerochaete chrysosporium bacterium solution are equably sprayed on alkali lignin, under ventilation condition fermentation obtain fermentation material；Fermentation material purifying；Fermentation material after purification is transferred in reactor tank after sulfonation and is centrifugated to obtain sediment with after dilute hydrochloric acid adjusting pH value to 2.0 by sulfonation；Alkalization is gradually added into sodium hydroxide solution until sediment dissolution, must be then to obtain clay grinding aid by solution concentration, crystallisation by cooling at 85 DEG C~90 DEG C in beaker.Compared to sodium lignin sulfonate, the grinding-aid effect of clay is significantly improved.
Description
Technical field
The present invention relates to mineral grinding technique fields, and in particular to a kind of clay grinding aid and preparation method thereof.
Background technique
Clay is a kind of important raw mineral materials, is aoxidized by a variety of hydrosilicates and a certain amount of aluminium oxide, alkali metal
Object and alkaline earth oxide composition, and contain the impurity such as quartz, feldspar, mica and sulfate, sulfide, carbonate.Clay
Mineral mainly include the mineral such as kaolinite race, illite race, montmorillonite race, vermiculite race and sepiolite group, and specific mineral have
Kaolinite, dickite, galapectite, nacrite, montmorillonite, hydromica etc., most of is that flakey, flake or tubulose are tiny
Crystal grain.The particle of clay mineral is tiny, is in crystal or noncrystal often within the scope of colloid size, most of is sheet, few
Number is tubulose, rodlike.Clay mineral water-wet has plasticity after moistening, and can deform under smaller pressure and can keep former for a long time
Shape, and large specific surface area have elecrtonegativity on particle, therefore have good physical adsorbability and chemical mobility of the surface, have
With other abilities for exchange of cation, therefore 10% or so can be added in glaze in ceramic industry to improve the suspension of glaze slip
Property.In addition, clay is also a kind of important source material of ceramic body.
Industrial clay mine has kaolin, bentonite (main group becomes montmorillonite), hydromica, illite, pyrophillite etc.
Deng, processing mostly uses wet processing greatly, i.e., ore through raw ore, be crushed, smash slurry, desanding, cyclone classification, grinding (delaminating),
Centrifuge is classified, magnetic separation (or bleaching), concentration, filters, finally spray-dried to obtain product.
Wherein, grinding is a poor efficiency, the process of highly energy-consuming, is taken a long time, power consumption Yue Dian ceramics factory
The 30% of total power consumption, but its efficiency is only 1% even lower, most input energies is for generating heat, useless
Impact, extruding, abrasion, electrostatic energy, elasticity and plasticity deformation and noise etc..It is thus typically necessary to which clay grinding aid is added to drop
Low milling time improves grinding efficiency.Therefore need to be added grinding aid during the grinding process to improve grinding aid efficiency.
It is usual to the mechanism of action of grinding aid that there are two types of representative theories.The first is " inhaling headed by Lie Binjieer
The absorption of attached reduction hardness " theory, i.e. clay grinding aid agent molecule on particle reduces the surface free energy of particle, or causes
The dislocation migration of lattice surface generates point defect or line defect to reduce the intensity and hardness of particle and promotes the generation of crackle
And extension, thus ore grinding energy consumption is reduced, improve grinding efficiency.It is for second " the Pulp Rheology headed by Crane Paar
Adjust " theory, it is believed that clay grinding aid can reduce slurry by rheological property and the Surface electric property etc. for adjusting slurry
Viscosity, promotes the dispersion of particle, to improve the mobility of slurry, prevent between particle, particle and abrasive media and liner plate it
Between reunion and adherency.The mechanism of action of clay grinding aid can be summarized as follows: 1. reduce crushing energy；2. increasing brittle fracture probability
To prevent from being plastically deformed；3. preventing fine grain flocculation and reassociating, strengthen dispersion；4. adjusting the rheological behavior of ore pulp.
Grinding aid is generally divided into inorganic grinding aid and Organic Grinding Aid.Inorganic grinding aid includes sodium tripolyphosphate, waterglass
Deng.Organic Grinding Aid is usually surfactant, including cationic surfactant, anionic surfactant, non-ionic
Organic active agent and amphoteric surfactant.In general, the polar group of surfactant can be adsorbed on particle surface
ξ electric potential is reduced, steric hindrance can also be formed by organic molecule chain, and then improve dispersion effect, prevent particle accumulation.
Wherein, anionic surfactant uses at most, such as sodium lignin sulfonate, neopelex, sodium citrate etc..
The fineness requirement of glaze clay is higher at present, and the generally wet-milling in grinding, technique requires general require
D99.5Less than 62.5 μm (225 mesh).Its inorganic grinding aid that 0.3wt% or so is usually added into wet-milling, including tripolyphosphate
Sodium, sodium pyrophosphate and waterglass etc..The grinding-aid effect of these grinding aids is more general, the wet-milling time be 14 hours with
On, expend mass energy.
Sodium lignin sulfonate is a kind of important surfactant, is chiefly used in cement grinding aid.As its primary raw material
Lignin is then mainly made after removing cellulose, phenols, carbohydrate using the black liquor generated in the digestion process of paper industry, right
Environmental protection and sustainable development are of great significance.There are acid-precipitation method, ultrafiltration using the method that black liquid extracts lignin
And flocculation sedimentation, lignin is sulfonated again to obtain sodium lignin sulfonate afterwards.The purity of the commercial wood element of top grade at present
It is only capable of reaching 70% or so, molecular weight limits its dispersion effect 200 to 10000 or so.
For lignin as a kind of larger molecular organics, structure is sufficiently complex, usually by more wound based structures, lilac base junction
Structure and these three structural units of p-hydroxyphenyl structure are coupled to complicated three-dimensional structure by ehter bond and carbon key mode, wherein β-O-
4 type bind modes can account for 50% or so.The dispersion degree of lignin is greater than 2, is tridimensional network.In electron microscope
Under, lignin be it is spherical or blocky, this largely limits the peptizaiton of lignin.
Wherein, lignin degradation method mainly passes through is aoxidized using chemical oxidizing agent (such as persulfate, oxygen, ozone)
In addition degradation, electrolysis method degradation can also pass through actinomyces door (Actinobacteria), Proteobacteria (Proteobacteria)
With the bacterial degradations such as Firmicutes (Firmicutes).For example, Phanerochaete chrysosporium (Phanerochaete
Chrysosporium) be white-rot fungi generate lignin-degrading enzymes and degrade persistence organic pollutant research type culture,
It has preferable degradation to lignin.CN105858913A discloses a kind of strong using Phanerochaete chrysosporium biology
The method for changing processing pulp-making waste-water, to reduce COD and BOD and the decoloration of waste water, and achieves preferable technical effect, but only
It is simple to handle waste water and do not improve its utility value.Master thesis " the modified alkali of electrolysis method of the Xie Ziyang of Guangzhou University
Lignin and performance evaluation " discloses a kind of method of electrolysis method modified alkali lignin, anti-by the free radical in electrolyte
It should degrade to it, but the only simple utility value for improving lignin itself.
Summary of the invention
How the technical problem to be solved by the present invention is to provide a kind of preparation method of clay grinding aid, prepare it
Clay grinding aid can better meet the grinding aid requirement of clay, as far as possible reduction milling time, reduction energy consumption.
The present invention solve technical problem the technical solution adopted is that: a kind of preparation method of clay grinding aid, comprising steps of
Alkali lignin purifying: by alkali lignin be added to by Isosorbide-5-Nitrae-dioxane and water preparation in the mixed solvent, slightly
Heating adjusts pH to 5.0~5.5, stands, then solution is centrifuged, obtain after being then vigorously stirred to promote to dissolve
Solid sample it is vacuum dried after the alkali lignin that is purified；
Microbial fermentation: preparation Phanerochaete chrysosporium bacterium solution and culture solution；By purified alkali lignin heap in fermentation
In slot and turn over it is even, turn over it is even during successively culture solution, Phanerochaete chrysosporium bacterium solution are equably sprayed on alkali lignin,
Then fermentation obtains fermentation material under ventilation condition；
Fermentation material purifying: fermentation material is added to the in the mixed solvent by Isosorbide-5-Nitrae-dioxane and water preparation, mild heat
After filter, adjust the pH to 5.0~5.5 of filtrate, stand, then solution is centrifuged, obtain after being then vigorously stirred
The fermentation material purified after solid sample is vacuum dried；
Sulfonation: fermentation material after purification is transferred in reactor tank after sulfonation and is centrifuged with after dilute hydrochloric acid adjusting pH value to 2.0
Sediment is separated to obtain, is transferred in beaker after then repeatedly washing sediment；
Alkalization: at 85 DEG C~90 DEG C, sodium hydroxide solution is gradually added into until sediment dissolution, then dense by solution
Contracting, crystallisation by cooling must be to obtain clay grinding aid.
Preferably, the alkali lignin purification step are as follows: the mixed solvent for preparing Isosorbide-5-Nitrae-dioxane and water is with quality
It is configured to 8~10kg of mixed solvent than 1.5~2:1,10kg alkali lignin and mild heat is added to promote to dissolve, is then added dropwise
The H of 3~5wt%2SO4Then pH value of solution is vigorously stirred after 2~5min and stands 3~4h to 5.0~5.5, then by solution carry out from
Heart separation, takes supernatant liquor to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxane, after obtained solid sample is vacuum dried
The alkali lignin purified.
Preferably, the microbial fermentation step are as follows: 100~150gNa is dissolved in 1L potato extracting solution2HPO4, 40
~80g KH2PO4, 20~30g NaCl, 10~20g NH4Culture solution is obtained after Cl and 300~400g glucose；It will be purified
Alkali lignin heap in fermentation tank and turn over it is even, turn over it is even during successively by the potato extracting solution, yellow archespore Mao Pingge
Bacterium bacterium solution is uniformly sprayed on alkali lignin, obtains fermentation material, fermentation process after then fermenting 20~25 days under ventilation condition
In every turning in 3~5 days it is primary, turning while uniformly spray glucose sugar juice 500 that mass fraction is 20~40wt%~
1000g。
Preferably, Phanerochaete chrysosporium bacterium solution is obtained by following methods: Phanerochaete chrysosporium is inoculated with from inclined-plane
Into the potato extracting liq culture medium of 500mL conical flask, bacteria suspension is made, 37 DEG C of constant temperature at shaking table culture three to four days.
Preferably, the sulfonation procedure includes: that fermentation material after purification is transferred in reactor tank by (1), and addition 100~
150kg deionized water, 40~50g solid sodium hydroxide stir to dissolve fermentation material, reacting liquid temperature are warming up to 50~55
DEG C, pH to 5.0~5.5 is adjusted with 0.1~0.3mol/L sodium hydroxide solution and 0.1~0.3mol/L hydrochloric acid solution, it is added 2~
20%~30% hydrogen peroxide of 2.5kg, the ferrous sulfate of 0.9~1kg react 50~70min, add 100~120g solid
Sodium hydroxide terminates reaction；(2) 70~75 DEG C are continuously heating to and 0.1~0.3mol/L sodium hydroxide solution adjusting pH value is added
To 9.0, formaldehyde that molar ratio is 1:1~1:3 and diethanol amine totally 400~450g is added, is stirred to react 1~1.5h；(3) continue
Be warming up to 90 DEG C, the sodium sulfite that 3~4kg is added reacts 40~60min, be then allowed to stand and be cooled to room temperature, then with 0.1~
0.3mol/L salt acid for adjusting pH value is transferred to beaker after then repeatedly washing sediment to sediment is centrifugated to obtain after 2.0
It is interior.
The present invention also provides a kind of clay grinding aids, are made by any of the above-described method.
The present invention can be improved its dispersion degree and carboxyl contain by carrying out purification and appropriate biodegrade to alkali lignin
Amount, is purified, after sulfonation, compared to sodium lignin sulfonate, grinding-aid effect is significantly improved again.When it is as clay grinding aid
With 0.3%~0.7% additive amount in use, the wet-milling time can be substantially reduced, reduce power consumption.
Detailed description of the invention
Fig. 1 is 1~3# clay grinding aid and sodium lignin sulfonate of the invention with the time-division in 0.3% dosage addition kaolin
The D not measured99.5- milling time relational graph；
Fig. 2 is the D measured when 2# clay grinding aid of the invention is added in pyrophillite clay with three kinds of different amounts99.5—
Milling time relational graph；
Fig. 3 is the D measured when 2# clay grinding aid of the invention is added in illite clay with three kinds of different amounts99.5—
Milling time relational graph；
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Wherein, Phanerochaete chrysosporium (P.Chrysosporium) can be managed by Chinese industrial Microbiological Culture Collection
Center is commercially available, and product number can be CICC40299, or CICC14076.
Phanerochaete chrysosporium bacterium solution is obtained by following methods: Phanerochaete chrysosporium is inoculated into 500mL from inclined-plane
In the potato extracting liq culture medium (potato extracting solution 1.0L, glucose 20.0g, agar 15.0g) of conical flask, bacterium is made
Suspension, 37 DEG C of constant temperature at shaking table culture three to four days.Wherein, potato extracting solution is prepared as follows: taking peeled potatoes
200g is cut into small pieces, and water 1.0L is added to boil 30min, filters off potato ball, filtrate is complemented to 1.0L.
Embodiment 1:
Alkali lignin purifying: being configured to mixed solvent 10kg for Isosorbide-5-Nitrae-dioxane and water with mass ratio 1.5:1, is added
Simultaneously then the H of 4wt% is added dropwise to promote to dissolve in mild heat to 10kg alkali lignin2SO4Then pH value of solution is vigorously stirred to 5.0
3.5h is stood after 2min, then solution is centrifuged, and takes supernatant liquor to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxy six
Ring, the alkali lignin 5.350kg purified after obtained solid sample is vacuum dried；
Microbial fermentation: 150gNa is dissolved in 1L potato extracting solution2HPO4, 40gKH2PO4, 30gNaCl, 20gNH4Cl
And 350g glucose obtains culture solution；By purified alkali lignin heap in fermentation tank and turn over it is even, turn over it is even during successively
Culture solution, Phanerochaete chrysosporium bacterium solution are uniformly sprayed on the alkali lignin in fermentation tank, then issued in ventilation condition
Ferment obtains fermentation material after 20 days, every turning in 3 days is primary in fermentation process, and it is 40wt% that turning while, which uniformly sprays mass fraction,
Glucose sugar juice 500g；
Fermentation material purifying: Isosorbide-5-Nitrae-dioxane and water are configured to mixed solvent 10kg with mass ratio 1.5:1, are added above-mentioned
It is filtered after fermentation material and mild heat 5min, the H of 4wt% is then added dropwise in filtrate2SO4Then pH value of solution is acutely stirred to 5.0
3.5h is stood after mixing 2min, then solution is centrifuged, takes supernatant liquor to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxy
Six rings, the fermentation material 4.613kg purified after obtained solid sample is vacuum dried；
Fermentation material again after purification: (1) being transferred in reactor tank by sulfonation, and 120kg deionized water, 50g solid is added
Sodium hydroxide stirs to dissolve fermentation material, reacting liquid temperature is warming up to 50 DEG C, with 0.3mol/L sodium hydroxide solution and
0.2mol/L hydrochloric acid solution adjusts pH to 5.2, and 30% hydrogen peroxide of 2kg, the ferrous sulfate reaction 50min of 0.95kg is added,
It adds 100g solid sodium hydroxide and terminates reaction；(2) 72 DEG C are continuously heating to and 0.1mol/L sodium hydroxide solution tune is added
PH value is saved to 9.0, the formaldehyde and the total 400g of diethanol amine that molar ratio is 1:3 is added, is stirred to react 1.5h；(3) it is continuously heating to
90 DEG C, the sodium sulfite reaction 50min of 4kg is added, is then allowed to stand and is cooled to room temperature, then use 0.3mol/L salt acid for adjusting pH
Value is transferred in beaker after then repeatedly washing sediment to sediment is centrifugated to obtain after 2.0；
Alkalization: under 90 DEG C of water bath conditions, sodium hydroxide solution is gradually added into beaker until keeping sediment all molten
Then solution concentration, crystallisation by cooling are obtained 1# clay grinding aid 4.971kg by solution.
Embodiment 2:
Alkali lignin purifying: being configured to mixed solvent 8kg for Isosorbide-5-Nitrae-dioxane and water with mass ratio 1.8:1, is added
Simultaneously then the H of 5wt% is added dropwise to promote to dissolve in mild heat to 10kg alkali lignin2SO4Then pH value of solution is vigorously stirred to 5.3
4h is stood after 4min, then solution is centrifuged, and supernatant liquor is taken to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxane,
The alkali lignin 5.361kg purified after obtained solid sample is vacuum dried；
Microbial fermentation: 100gNa is added in 1L potato extracting solution2HPO4, 60gKH2PO4, 20gNaCl, 10gNH4Cl
And 400g glucose, culture solution is obtained after dissolution；By purified alkali lignin heap in fermentation tank and turning over even, even process is being turned over
In successively culture solution, Phanerochaete chrysosporium bacterium solution are uniformly sprayed on the alkali lignin in fermentation tank, then in air duct slats
Fermentation material is obtained after fermenting 23 days under part, every turning in 4 days is primary in fermentation process, and turning while uniformly sprays mass fraction and is
The glucose sugar juice 1000g of 20wt%；
Fermentation material purifying: Isosorbide-5-Nitrae-dioxane and water are configured to mixed solvent 8kg with mass ratio 1.8:1, are added above-mentioned
It is filtered after fermentation material and mild heat 4min, the H of 5wt% is then added dropwise in filtrate2SO4Then pH value of solution is acutely stirred to 5.3
4h is stood after mixing 4min, then solution is centrifuged, takes supernatant liquor to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxy six
Ring, the fermentation material 4.708kg purified after obtained solid sample is vacuum dried；
Fermentation material again after purification: (1) being transferred in reactor tank by sulfonation, and 150kg deionized water, 40g solid is added
Sodium hydroxide stirs to dissolve fermentation material, reacting liquid temperature is warming up to 52 DEG C, with 0.1mol/L sodium hydroxide solution and
0.3mol/L hydrochloric acid solution adjusts pH to 5.5, and 20% hydrogen peroxide of 2.3kg, the ferrous sulfate reaction 60min of 1kg is added, then
110g solid sodium hydroxide is added and terminates reaction；(2) 75 DEG C are continuously heating to and the adjusting of 0.2mol/L sodium hydroxide solution is added
PH value is added the formaldehyde and the total 450g of diethanol amine that molar ratio is 1:1, is stirred to react 1h to 9.0；(3) 90 DEG C are continuously heating to,
The sodium sulfite that 3kg is added reacts 60min, is then allowed to stand and is cooled to room temperature, then extremely with 0.1mol/L salt acid for adjusting pH value
It is centrifugated to obtain sediment after 2.0, is transferred in beaker after then repeatedly washing sediment；
Alkalization: under 87 DEG C of water bath conditions, sodium hydroxide solution is gradually added into beaker until dissolving sediment, so
Solution concentration, crystallisation by cooling are obtained into 2# clay grinding aid 5.013kg afterwards.
Embodiment 3:
Alkali lignin purifying: Isosorbide-5-Nitrae-dioxane and water are configured to mixed solvent 9kg with mass ratio 2:1,10kg is added
Simultaneously then the H of 3wt% is added dropwise to promote to dissolve in mild heat to alkali lignin2SO4Then pH value of solution is vigorously stirred 5min to 5.5
After stand 3h, then solution is centrifuged, takes supernatant liquor to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxane, obtain
Solid sample it is vacuum dried after the alkali lignin 5.362kg that is purified；
Microbial fermentation: 120gNa is added in 1L potato extracting solution2HPO4, 80gKH2PO4, 25gNaCl, 15gNH4Cl
And 300g glucose obtains culture solution；By purified alkali lignin heap in fermentation tank and turn over it is even, turn over it is even during successively
Culture solution, Phanerochaete chrysosporium bacterium solution are uniformly sprayed on the alkali lignin in fermentation tank, then issued in ventilation condition
Ferment obtains fermentation material after 25 days, every turning in 5 days is primary in fermentation process, and it is 30wt% that turning while, which uniformly sprays mass fraction,
Glucose sugar juice 750g；
Fermentation material purifying: Isosorbide-5-Nitrae-dioxane and water are configured to mixed solvent 9kg with mass ratio 2:1,10kg hair is added
It is filtered after ferment material and mild heat 3min, the H of 3wt% is then added dropwise in filtrate2SO4Then pH value of solution is vigorously stirred to 5.5
3h is stood after 5min, then solution is centrifuged, and supernatant liquor is taken to be concentrated through thin film evaporation to recycle Isosorbide-5-Nitrae-dioxane,
The fermentation material element 4.790kg purified after obtained solid sample is vacuum dried；
Fermentation material again after purification: (1) being transferred in reactor tank by sulfonation, and 100kg deionized water, 45g solid is added
Sodium hydroxide stirs to dissolve fermentation material, reacting liquid temperature is warming up to 55 DEG C, with 0.2mol/L sodium hydroxide solution and
0.1mol/L hydrochloric acid solution adjusts pH to 5.0, and 25% hydrogen peroxide of 2.5kg, the ferrous sulfate reaction 70min of 0.9kg is added,
It adds 120g solid sodium hydroxide and terminates reaction；(2) 70 DEG C are continuously heating to and 0.3mol/L sodium hydroxide solution tune is added
PH value is saved to 9.0, the formaldehyde and the total 450g of diethanol amine that molar ratio is 1:2 is added, is stirred to react 75min；(3) it is continuously heating to
90 DEG C, the sodium sulfite reaction 40min of 3.5kg is added, is then allowed to stand and is cooled to room temperature, then adjusted with 0.2mol/L hydrochloric acid
PH value is transferred in beaker after then repeatedly washing sediment to sediment is centrifugated to obtain after 2.0；
Alkalization: under 85 DEG C of water bath conditions, it is gradually added into sodium hydroxide solution in beaker until dissolving sediment, incites somebody to action
Solution, which is concentrated, crystallisation by cooling is dry obtains 3# clay grinding aid 5.225kg.
Grinding-aid effect test:
By raw clay 0.5t, 0.6 ton of water, steel ball 1.5t (steel ball of 120mm: Ф 80mm: Ф tri- kinds of specifications of 40mm of Ф with
Mass ratio 3:4:3 carries out gradation) it is placed in 900 × 1800 horizontal drum ball mill of Ф (fixed star heavy equipment Co., Ltd, Zhengzhou City)
In, while the grinding aid of certain mass is added, setting speed is 36~38r/min, and total wet-milling time is 16h.Before wet-milling and
At interval of (150 DEG C) are dried after 2h sampling during wet-milling, tested by 2000 type laser particle size analyzer of Mastersizer
Its size distribution obtains its D extremely according to size distribution99.5(grain diameter is in D99.5Quality accounting below is 99.5%) value.
Wherein, Fig. 1 is shown uses 1#~3# grinding aid of the invention and one hundred Hongxin Materials Co., Ltd in kaolin
D measured by the top grade sodium lignin sulfonate (being denoted as 0#) of production99.5Data.(grinding aid and clay are former for the dosage of its grinding aid
The mass ratio of material) it is 0.3%.From figure 1 it appears that kaolin wet is milled to D relative to addition sodium lignin sulfonate99.5
It is 62.5 μm or less required 15 hours or so times, grinding aid prepared by the present invention only needs 6 hours or so, saves big
Measure power consumption；Simultaneously with the extension of wet-milling time, D99.5Up to 20 μm or so.Wherein, when adding 2# grinding aid, in grinding
Between for D in 0~6h99.5Faster, grinding-aid effect is more excellent for decline.
In addition, Fig. 2 and Fig. 3 are also shown in kind adds difference in pyrophillite clay and illite clay respectively
The grinding-aid effect of the 2# grinding aid of dosage.Statistics indicate that, above-mentioned grinding aid of the invention is in addition to for kaolin shown in Fig. 2, Fig. 3
There is preferable grinding-aid effect, also can be well suited for pyrophillite clay and illite clay, the dosage of 2# grinding aid is 0.5%
In the case where, pyrophillite clay and illite clay only need wet-milling 8 hours or so can be levigate to D by clay99.5For 62.5 μ
M or less.
The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although referring to aforementioned each reality
Applying example, invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each
Technical solution documented by embodiment is modified, or equivalent substitution of some or all of the technical features；And
These are modified or replaceed, the range for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (6)
1. a kind of preparation method of clay grinding aid, which is characterized in that comprising steps of
Alkali lignin purifying: alkali lignin is added to the in the mixed solvent by Isosorbide-5-Nitrae-dioxane and water preparation, mild heat
To promote dissolution, pH to 5.0~5.5 is adjusted, is stood after being then vigorously stirred, then solution is centrifuged, what is obtained consolidates
The alkali lignin purified after body sample is vacuum dried；
Microbial fermentation: preparation Phanerochaete chrysosporium bacterium solution and culture solution；By purified alkali lignin heap in fermentation tank
And turn over it is even, turn over it is even during successively culture solution, Phanerochaete chrysosporium bacterium solution are equably sprayed on alkali lignin, then
Fermentation obtains fermentation material under ventilation condition；
Fermentation material purifying: fermentation material is added to the in the mixed solvent by Isosorbide-5-Nitrae-dioxane and water preparation, mistake after mild heat
Filter, adjusts the pH to 5.0~5.5 of filtrate, stands after being then vigorously stirred, then solution is centrifuged, obtained solid
The fermentation material purified after sample is vacuum dried；
Sulfonation: fermentation material after purification is transferred in reactor tank after sulfonation and is centrifugated with after dilute hydrochloric acid adjusting pH value to 2.0
Sediment is obtained, is transferred in beaker after then repeatedly washing sediment；
Alkalization: at 85 DEG C~90 DEG C, sodium hydroxide solution is gradually added into until solution, is then concentrated, is cold by sediment dissolution
But it crystallizes to obtain clay grinding aid.
2. the preparation method of clay grinding aid as described in claim 1, which is characterized in that the alkali lignin purification step
Are as follows: the mixed solvent that Isosorbide-5-Nitrae-dioxane and water are prepared is configured to 8~10kg of mixed solvent with 1.5~2:1 of mass ratio, is added
Simultaneously then the H of 3~5wt% is added dropwise to promote to dissolve in mild heat to 10kg alkali lignin2SO4PH value of solution is to 5.0~5.5, then
3~4h is stood after being vigorously stirred 2~5min, then solution is centrifuged, supernatant liquor is taken to be concentrated through thin film evaporation to return
Receive Isosorbide-5-Nitrae-dioxane, the alkali lignin purified after obtained solid sample is vacuum dried.
3. the preparation method of clay grinding aid as described in claim 1, which is characterized in that the microbial fermentation step are as follows:
100~150g Na is dissolved in 1L potato extracting solution2HPO4, 40~80g KH2PO4, 20~30g NaCl, 10~20g
NH4Culture solution is obtained after Cl and 300~400g glucose；By purified alkali lignin heap in fermentation tank and turning over even, turning over
Successively the potato extracting solution, Phanerochaete chrysosporium bacterium solution are uniformly sprayed on alkali lignin during even, then existed
Fermentation material is obtained after fermenting 20~25 days under ventilation condition, every turning in 3~5 days is primary in fermentation process, and turning while is uniform
Spray 500~1000g of glucose sugar juice that mass fraction is 20~40wt%.
4. the preparation method of clay grinding aid as described in claim 1, which is characterized in that Phanerochaete chrysosporium bacterium solution is by following
Method obtains: by Phanerochaete chrysosporium from the potato extracting liq culture medium for being inoculated into 500mL conical flask on inclined-plane, system
At bacteria suspension, 37 DEG C of constant temperature at shaking table culture three to four days.
5. the preparation method of clay grinding aid as described in claim 1, which is characterized in that the sulfonation procedure includes: that (1) will
Fermentation material after purification is transferred in reactor tank, and 100~150kg deionized water, 40~50g solid sodium hydroxide, stirring is added
To dissolve fermentation material, reacting liquid temperature is warming up to 50~55 DEG C, with 0.1~0.3mol/L sodium hydroxide solution and 0.1~
0.3mol/L hydrochloric acid solution adjusts pH to 5.0~5.5, and 20%~30% hydrogen peroxide of 2~2.5kg, 0.9~1kg is added
Ferrous sulfate reacts 50~70min, adds 100~120g solid sodium hydroxide and terminates reaction；(2) 70~75 are continuously heating to
DEG C and 0.1~0.3mol/L sodium hydroxide solution be added adjust pH value to 9.0, the formaldehyde and two that molar ratio is 1:1~1:3 is added
Ethanol amine totally 400~450g, is stirred to react 1~1.5h；(3) 90 DEG C are continuously heating to, the sodium sulfite reaction of 3~4kg is added
40~60min is then allowed to stand and is cooled to room temperature, then with being centrifugated after 0.1~0.3mol/L salt acid for adjusting pH value to 2.0
Sediment is obtained, is transferred in beaker after then repeatedly washing sediment.
6. a kind of clay grinding aid, which is characterized in that be made by method according to any one of claims 1 to 5.
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| CN116144324A (en) * | 2023-02-23 | 2023-05-23 | 湖南格林朗科技有限公司 | Synergistic liquid special for mineral separation and preparation method and application thereof |
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