CN105820350B - Phenolate methylolation and carboxy methylation lignin and preparation method thereof - Google Patents
Phenolate methylolation and carboxy methylation lignin and preparation method thereof Download PDFInfo
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- CN105820350B CN105820350B CN201610255792.6A CN201610255792A CN105820350B CN 105820350 B CN105820350 B CN 105820350B CN 201610255792 A CN201610255792 A CN 201610255792A CN 105820350 B CN105820350 B CN 105820350B
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Abstract
The invention discloses a kind of phenolate methylolation and carboxy methylation lignins and preparation method thereof, and wherein the preparation method of phenolate methylolation and carboxy methylation lignin includes the following steps: that (1) prepares phenolate lignin: lignin being carried out phenolate and is obtained phenolate lignin with phenol and acid；(2) preparation phenolate and hydro methylated lignin: the phenolate lignin is subjected to methylolation with aqueous slkali and aldehyde and obtains the hydro methylated lignin；(3) by the phenolate, simultaneously hydro methylated lignin progress carboxy methylation obtains phenolate methylolation and carboxy methylation lignin.The phenolate methylolation and carboxy methylation lignin of the method for the present invention preparation are water-soluble and adsorption of metal ions ability is all very strong, are suitable as chelated trace fertilizer use.
Description
Technical field
The present invention relates to lignin manufacture fields, and in particular to a kind of phenolate methylolation and carboxy methylation lignin and its system
Preparation Method.
Background technique
Liginon Resource is abundant, is typically used as water-reducing agent, binder and reinforcing agent etc., the functional group containing there are many, such as
Phenolic hydroxyl group, methoxyl group, ehter bond and carbonyl etc. are the desirable feedstocks as chelated trace fertilizer, however chelated trace fertilizer is to water-soluble and gold
Category ionic adsorption performance requirement is higher, and the water solubility of lignin is very poor, only has weaker adsorption of metal ions.
At present for the research of the adsorption of metal ions of lignin substantially based on chemical modification, such as pass through to
The method of the functional groups such as amino and sulfonic group is introduced in lignin；It is porous as matrix synthesis using lignin and rich in there are many function
The method of group's material；With the methods of lignin synthesis resin.However product majority obtained by the above method is insoluble in water, because
This product obtained by the above method is still not suitable as chelated trace fertilizer use.
Summary of the invention
The present invention provides a kind of phenolate methylolation and carboxy methylation lignin and preparation method thereof, the method for the present invention preparations
Phenolate methylolation and carboxy methylation lignin is water-soluble and adsorption of metal ions ability is all very strong, being suitable as chelated trace fertilizer makes
With.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides the preparation methods of a kind of phenolate methylolation and carboxy methylation lignin, include the following steps:
(1) it prepares phenolate lignin: lignin being subjected to phenolate and is obtained phenolate lignin with phenol and acid；
(2) preparation phenolate and hydro methylated lignin: the phenolate lignin is subjected to methylolation with aqueous slkali and aldehyde and is obtained
To the hydro methylated lignin；
(3) by the phenolate, simultaneously hydro methylated lignin progress carboxy methylation obtains phenolate methylolation and carboxy methylation wood
Element.
Further, the step (1) specifically comprises the following steps:
The lignin of 1 parts by weight is mixed with the phenol of 0.3-4 parts by weight and sulfuric acid solution is added thereto and is mixed
Liquid, the concentration of the sulfuric acid are 70%-98%, H in the mixed liquor2SO4Mass fraction be 0.5-10%；It boils
0.5-4h obtains the first sediment, and first drying precipitate is obtained the phenolate lignin.
Further, the step (2) specifically comprises the following steps:
The concentration that the phenolate lignin is dissolved in is then to be added and hold thereto in the sodium hydroxide solution of 1-4mol/L
It sets the formalin that mass fraction is 30-40% and reacts 0.5-3h；Phenolate lignin, sodium hydroxide solution and the formalin
Mass volume ratio be 1g:3-10mL:3-10ml；Then acidification, centrifugation obtain the second sediment, by second sediment
It is dried to obtain the phenolate and hydro methylated lignin.
Further, the acidification is that the hydrochloric acid solution for being 0-3 with pH value is acidified 10-60min.
Further, the step (3) specifically comprises the following steps: the phenolate hydro methylated lignin, isopropyl
Pure and mild sodium hydroxide is that 1g:10-60ml:1-4g hybrid reaction 0.5-2h obtains the first reaction solution according to mass volume ratio, by institute
The first reaction solution stated, which is warming up to 40-90 DEG C and chloroacetate reaction 0.5-3h is added thereto, obtains the second reaction solution, described to add
The 1-4:2 of the monoxone and phenolate hydro methylated lignin quality that enter；Chloroacetate reaction 0.5- is added into second reaction solution
3h obtains third reaction solution, and the mass ratio of the monoxone being added into the second reaction solution and phenolate hydro methylated lignin is
1-4:2；Then the pH value for adjusting third reaction solution is 5-8, removes substance of the molecular weight less than 3500, is drying to obtain the phenol
Change methylolation and carboxy methylation lignin.
Further, substance of the removing molecular weight less than 3500 uses dialysis.
Further, the drying is to be lyophilized in freeze drier.
On the other hand, the present invention provides a kind of phenolate methylolation and carboxy methylation lignins, which is characterized in that described
Simultaneously carboxy methylation lignin is prepared phenolate methylolation by above-mentioned method, the phenolate methylolation and carboxy methylation wood
The water-soluble rate of element is 50%-90%, and the adsorbance to zinc ion is 90-180mg/g.
Compared with prior art, the present invention at least has the following beneficial effects:
The present patent application is by having carried out phenolate and methylolation processing for lignin, so that the active site of lignin increases
Add, there is subsequent carboxy methylation to handle, improves the effect of carboxy methylation processing by increasing active site, so that after processing
The phenolate methylolation and carboxy methylation lignin arrived has good water-soluble and adsorption of metal ions ability.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of L, PL, CPL and CHPL；
Fig. 2 is the thermal gravimetric analysis curve of L and CPL；
Fig. 3 is sample dissolution rate histogram；
Fig. 4 is L dispersed image in water；
Fig. 5 is CPL dispersed image in water；
Fig. 6 is CHPL dispersed image in water；
The sediment fraction of Fig. 7 L, CPL and CHPL, adsorbance and total adsorbance column of the water-soluble portion to zinc ion
Figure；
Fig. 8 is L, the potentiometric titration curve of CPL, CHPL and water；
Fig. 9 is L, Zn2+And L-Zn2+Potentiometric titration curve；
Figure 10 is CPL, Zn2+And CPL-Zn2+Potentiometric titration curve；
Figure 11 is CHPL, Zn2+And CHPL-Zn2+Potentiometric titration curve.
Specific embodiment
For the technical solution that the present patent application is more clearly understood convenient for those skilled in the art, below with reference to preferable reality
It applies example to be further elaborated the present patent application, it should be understood that preferred embodiment is not as the restriction to the present patent application.
The principle of the present patent application is to be handled by phenolate and methylolation so that the active site of lignin sufficiently exposes,
To make lignin obtain preferable water-soluble and adsorption of metal ions so that the processing of subsequent carboxy methylation can be carried out sufficiently
Property.
Sulfuric acid used in following embodiment, phenol, formaldehyde, sodium hydroxide, monoxone, isopropanol, zinc chloride are point
Analyse pure, experiment whole process with water is deionized water.
Constant temperature blender with magnetic force, 50 and 100mL three-necked flask, freeze drying equipment, III type elemental analyser of vario EL,
750 type Fourier infrared spectrograph of Nicolet, 2500 type fluorescence microscope of LEICA DM, DTG-60 type thermogravimetric analyzer, ET
18 type potentiometric titrimeters, 5000 type Atomic Absorption Spectrometer of Z etc..
Here is specific embodiment
Corncob industrial lignin is provided by the Shandong biotech inc Long Li.Production process is as follows: corn
Core obtains xylan by hydro-thermal process degradation of hemicellulose.Residue carries out alkali process and reaches removing lignin and obtain solid
The purpose of cellulose residue.Raw material of the cellulose as production bio-ethanol, the lignin in waste liquid are obtained by acid precipitating
Industrial alkali lignin.Its total lignin content 94.42%, carbohydrate content 0.63%, ash content 2.16%.
(1) lignin phenolate
1.0g industry alkali lignin and 2g phenol are blended in 50mL three-necked flask and the sulfuric acid of addition 72% makes its quality
Score accounts for 6.7%, stirs 20 minutes at 110 DEG C.Then it is transferred to 1000mL flask and 560mL deionized water is added, terminate reaction,
Suspension is boiled into 3h.It filters while hot and is sufficiently washed to precipitate to dry sediment at 60 DEG C with warm water and obtain phenolate lignin
(PL).Product is ground into mixing in triplicate, is saved backup.
(2) by phenolate lignin methylolation:
1.0g phenolate lignin is put into the sodium hydroxide that addition 10mL concentration is 2mol/L in 50mL three-necked flask and is dissolved,
Then magnetic agitation under the conditions of 60 DEG C, reaction be initially added into 37% formaldehyde 10mL, 2h after formaldehyde 10mL is added again again
React 2h.Reaction terminates to be acidified with the HCl that pH is 1,3900 revs/min, under the conditions of be centrifugated 5 minutes and the desalinization of soil by flooding or leaching 3 times, it is heavy
Starch is freeze-dried to obtain phenolate and hydro methylated lignin (HPL).
(3) by phenolate and hydro methylated lignin progress carboxy methylation processing:
Carboxymethyl-modification reaction is designed with reference on the basis of modified waste paper and modified sulphonate lignin.1g HPL
It is put into addition 60mL isopropanol in the three-necked flask of 100mL, 3.6g NaOH is then added, 1h is stirred at room temperature.Then 40 are warming up to
DEG C, it is added after 1g chloroacetate reaction 2h and adds 1g monoxone the reaction was continued 2h, react whole 150 revs/min of magnetic agitation.Reaction
The pH for the hydrochloric acid regulation system for being 1 with pH after 4h is 7.Then molecular weight is less than to the salinity of 3500g/mol with the method for dialysis
It is removed with unreacted impurity, every 8h changes a water, dialyses five days.Sample in bag filter is lyophilized to obtain CHPL, equally
1g PL carries out carboxymethyl-modification under identical experiment condition and reacts to obtain CPL as control experiment.
To obtained phenolate methylolation and carboxy methylation lignin
(1) characterization measurement is carried out to obtained CPL:
Infrared spectrum analysis (FTIR)
It takes five kinds of samples of L, PL, HPL, CPL, CHPL a small amount of, is dried in 105 DEG C of baking ovens, then the tabletting system together with KBr
It is standby at infrared scan sample, with 750 type Fourier infrared spectrograph of Nicolet in 400-4000cm-1It scans and records in range
Infrared spectrogram.
Elemental analysis
The sample of progress elemental analysis includes (PL, HPL, CPL, the CHPL) that unreacted lignin (L) and modified-reaction obtain
Sample first passes through 105 DEG C of oven dryings, and carbon, hydrogen, nitrogen are then carried out under CHN mode with III type elemental analyser of Vario EL
The analysis of element.Remainder is considered as oxygen element (100%-C%-H%-N%).
Thermogravimetric analysis (TGA)
The sample of unreacted lignin (L) and modified lignin (CHPL) carries out thermogravimetric analysis with DTG-60 type thermogravimetric analyzer,
The sample of about 7.5mg is used to record and rises with temperature, the weight-loss curve and first derivative curve of sample.Test condition,
Nitrogen flow rate 50mL/min is raised to 800 DEG C from room temperature with the heating rate of 10 DEG C/min.
Dissolubility and water-dispersible granule analysis
The sample of unreacted lignin (L) and modified lignin (CPL, CHPL) is used for dissolubility analysis and water-dispersible granule
The comparison of size.0.1g sample is packed into 50mL centrifuge tube and 20mL deionized water is added, and vibrates 1h on round-trip oscillator at room temperature.
Each sample takes out coherent condition of two drops in 2500 type fluorescence microscopy microscopic observation sample particle of LEICA DM in water.So
The effective centrifuge of centrifugation of sample will be housed afterwards, be centrifuged with 3500 revs/min of revolving speed, pour out solvent portions above
Precipitating is subjected to drying weighing.The dissolution rate for calculating different samples, is averaged in triplicate.Sample is calculated using formula (1)
Dissolution rate a:
A: the dissolution rate of lignin, Wt: the quality of lignin, Ws: the quality of lignin deposit part；
Measurement of the modified sample to zinc ion adsorbance
In order to probe by sample dissolubility and to the combination of adsorption of metal ions property, each sample passes through centrifuge separation
It is divided into sediment fraction and water-soluble portion.Each sample different component about 0.05g is put into 20mL containing Zn2+0.05mol/L, pH 6
System in.It vibrates at room temperature for 24 hours.Then mixed liquor is transferred completely into the bag filter that dialysis molecular weight is less than 3500g/mol
In, it is primary to change water by every 8h in the beaker of 1000mL, dialyses five days altogether, removes unadsorbed zinc ion.It will be in bag filter
Liquid is transferred in 50mL triangular flask and is dried in 105 DEG C of baking oven, and 5mL mixed acid (HNO is then added33mL, HCLO4
It 2mL) is cleared up with electric hot plate low-temperature heat, until digestion solution, is then transferred to by the liquid of residue about 1mL clear
In 50mL volumetric flask and constant volume, with 5000 type atomic absorption spectrometry of Z and different sample different components are calculated to zinc ion
Adsorbance.
Adsorbance (Adsorption amount) (Qe/mg g-1) calculating according to following formula (2-4):
Qt=Qs × (1-a)-Q1 × a (4)
QS: sample pellet part is to Zn2+Adsorbance, Q1: sample water-soluble portion is to Zn2+Adsorbance, Qt: it calculates
Sample to Zn2+Total adsorbance, a: the dissolution rate of sample, c1: the Zn of sediment fraction measurement2+Concentration, v1: sediment fraction is corresponding
Reference extension rate conversion total liquid volume, m1: the quality of sediment fraction sample component, c1: the measurement of sample water-soluble portion
Zn2+Concentration, v1: the corresponding total liquid volume to convert with reference to extension rate of sample water-soluble portion, m1: sample water solubility portion
Divide the quality of sample component.
Potential Titration Analysis
Automatical potentiometric titrimeter (METTLER TOLEDO ET18) is used to test the acidity of different samples and for exploring
Chelating behavior of the different samples to zinc ion.Using hydrochloric acid to adjust deionized water pH is 1.6 as solvent, and test sample is divided into:
It is that analysis sample (L, CPL and CHPL), pH 1.6 are respectively formed in 1.6 water that L, CPL and CHPL of 0.05g, which is dispersed in 25ml pH,
Deionized water dissolving zinc chloride make the concentration 0.05mol/L of zinc ion, form sample to be analysed (Zn2+) and it is molten as zinc
0.05g is added in liquid, the zinc solution that 25mL pH is 1.6, and L, CPL and CHPL are respectively formed analysis sample (L-Zn2+、CPL-Zn2+With
CHPL-Zn2+).The deionized water that 25mLpH is 1.6 forms analysis sample (H as control2O).Deionization is adjusted with sodium hydroxide
The pH of water is 11.5 as titrating solution.It is mapped with the pH change curve of the different samples of addition with alkali.
(2) result and analysis
Infrared spectrum characterization before and after lignin modification
What Fig. 1 was presented is lignin and modified lignin in 700-4000cm-1Infrared spectroscopy, wherein representated by lines 1
It is phenolate and carboxy methylation wood representated by lines 2 for phenolate methylolation and the infrared spectroscopy of carboxy methylation lignin (CHPL)
The infrared spectroscopy of plain (CPL) is the infrared spectroscopy of phenolate and hydro methylated lignin (HPL), 4 generations of lines representated by lines 3
Table is the infrared spectroscopy of phenolate lignin (PL), is the infrared spectroscopy of lignin (L) representated by lines 5.1602,1504 Hes
1454cm-1Because phenyl ring vibrates, L is weaker in the absorption of these peak positions for the absorption at place, this may is that the fragrance knot because in lignin
Structure is in the industrial production by certain destruction.The phenyl ring of PL vibrates enhancing after phenolate processing, illustrates that phenyl ring successfully introduces
Into lignin structure.2929cm-1The absorption at place is the C-H stretching vibration due to methyl and methylene, CPL and CHPL have herein compared with
Strong absorption may is that because carboxymethyl-modification forms more methylene.The stretching vibration of C=O is in 1900-1650cm-1
In wave-length coverage, because strong hydrogen bond action absorption peak can be mobile to low wavelength direction.Since L, PL, HPL contain C=O, all
In 1700cm-1Nearby there is an absorption, CHPL and CPL are compared with L, PL, HPL in 1700cm-1The absorption peak at place disappears, but new appearance
Absorption peak 1605cm-1And 1420cm-1Show the presence of carboxyl.1605 and 1420cm-1The absorption power at place is used to show carboxyl
The number of content, with lignin after phenolate compared with direct carboxymethyl-modification (CPL), further methylolation carboxylic first again after phenolate
Baseization modified (CHPL) can greatly improve sample in 1605 and 1420cm-1The absorption intensity at place, this also indicates that CHPL is introduced
More carboxyls.1000-1100cm-1Place is the absorption of C-O-C, 1030cm-1Place CHPL and CPL has stronger absorption compared with L,
It is because carboxymethyl-modification generates many ehter bonds.1200cm-1C-O stretching vibration of the absorption due to methoxyl group, 1335cm-1It is the wagging vibration of hydroxyl or methylene.3500cm-1It is the vibration of hydroxyl.Infrared spectrum characterization results showed that
The success of each step modified-reaction.
Elemental analysis
Table 1 be elemental analysis as a result, in table 1 statistics indicate that, unmodified lignin (L) carbon containing 60.0%, oxygen 33.8%,
Hydrogen 5.2%.Phenol, CH3OH, CH3The ratio of the C:H:O of COOH is respectively 76.6:6.4:17,12:4:16,6:1:8.It is modified
The variation of functional group can be intuitively reflected in the variation of element.
The elemental analysis of table 1 modified lignin resin and unmodified lignin
Compared with L, the carbon content of PL lignin increases and oxygen content reduces, this is because the phenyl ring introduced has a high C/
O ratio.Hydroxymethylation and carboxymethylation reaction can all introduce the functional group of lower C/O ratio, therefore compared with PL, HPL, CPL
It is all cashed with CHPL as carbon content reduction and oxygen content raising.Sample element variation intuitively reacted modified-reaction at
Function.
Thermogravimetric analysis
Thermal gravimetric analysis results are as shown in Figure 2, wherein 6 be the weight loss of L, and 7 be the weight loss of CHPL, and 8 be the weight of L
Amount loss rate, 9 be the rate of weight loss of CHPL, and two kinds of samples all show the weight loss of three phases as can be seen from Figure 2.
First stage is within the scope of 40-250 DEG C, due to the loss of sample aqueous vapor and volatile substances.Compared with lignin (L), finally
Modified product (CHPL) be lower than 250 DEG C when show more weight loss, this is because modified-reaction draws into lignin
More hydrophilic functional group is entered, CHPL absorbs more steam indoors before entering analysis.
When temperature is higher than 250 DEG C, the loss of weight is the decomposition due to polymer.Unmodified lignin (L) is in 250-450
About 50% weight loss between DEG C.For CHPL, about 22% weight loss between 300-450 DEG C.CHPL exists
Quality at 800 DEG C with 45% remains, and unmodified lignin only has the quality residual less than 10%.With unmodified lignin (L)
It compares, the pyrolysis activation energy of CHPL improves, this is because carboxymethyl-modification generates the good ehter bond of thermal stability.
Dissolubility and water-dispersible granule analysis
Water-soluble result is as shown in figure 3, unmodified lignin (L) has low-down water-soluble (being lower than 8.7%), in fact
The light component that some in lignin suspend is limited by method and has been counted as soluble part, and the water-soluble rate of CPL is 34.7%, CHPL water
The preferably water-soluble rate of dissolubility is 69.7%.Show to introduce largely by phenolate, two step pre-treatment of methylolation, then carboxymethyl-modification
Carboxyl largely improves the water solubility of material.
Fig. 4,5 and 6 are respectively the L that observes under fluorescence microscope, CPL, the figure of CHPL sample dispersity in water
Picture.From Fig. 4,5 and 6 as can be seen that the particle of lignin sample is larger, diameter range is 0-80 μm, and concentrates on bulky grain,
Since the hydrophobicity of lignin makes lignin be easy to be gathered into bulky grain in water.Compared with lignin, the sample particle diameter of CPL and CHPL compared with
Small distribution is 0-20 μm, and based on fine particle.In addition observing has dark-coloured patch, table in the image of L and CPL
It is bright there is no lignin components at these dark-coloured visuals field, in the image of CHPL dark-coloured patch disappear and also entire background fluorescence intensity compared with
By force, illustrate that the water-soluble little particle of CHPL has been uniformly dispersed in water.The particle of CPL and CHPL is small, is on the one hand because of parent
Aqueous functional group increases, and on the other hand may be to make small because the introducing of carboxyl keeps modified product particle surface charging property identical
It is mutually exclusive between particle to cause to disperse.Carboxyl can be used as the stabilizer of CPL and CHPL internal particle, because carboxyl passes through-O-
C- or-C-O-C- is connected with aromatic rings, and the carboxyl in polymer carbon tends to the surface for being distributed in polymer beads.Be because
For compared with CPL and L, CHPL particle surface possesses more carboxyl and it is made to have preferable water-soluble and dispersibility.
Modified sample analyzes the adsorption experiment of zinc ion
Fig. 7 is the sediment fraction of L, CPL and CHPL, water-soluble portion to the adsorbance and total adsorbance of zinc ion, by
Fig. 7 is it is found that the water-soluble component of three kinds of modified products is all larger than sediment fraction to the adsorbance of zinc ion.Lignin water-soluble component
There is different structure and property from deposited components, hydrophilic functional group's content of solvent portions is high, and these functional groups also have
Conducive to the absorption to zinc ion.The sediment fraction of unmodified lignin only has 50.5mg/g to the adsorbance of zinc ion, and CPL and
The sediment fraction of CHPL is respectively 101.6mg/g and 120mg/g to the adsorbance of zinc ion.It may be since chemical modification changes
The introducing of the functional group of sediment fraction, especially carboxyl enhances CPL and CHPL to the adsorption capacity of zinc ion.L, CPL and
The water-soluble component of CHPL is respectively 88.4,134.7 and 126.1mg/g, the adsorbance of CPL and CHPL to the adsorbance of zinc ion
Between difference it is not significant but be all remarkably higher than L.L, CPL and CHPL is respectively 53.8,113.3 to zinc ion adsorbance,
122.3mg/g, CHPL each component all have biggish zinc ion adsorbance and water-soluble component content is more, and consolidated statement reveals most
Good zinc ion adsorption capacity.
Potential Titration Analysis
The important information that Potential Titration Analysis can provide includes the content of material surface functional group and the soda acid of functional group
Property.Fig. 8 is the potentiometric titration curve of L, CPL, CHPL and water, and as can be seen from Figure 8, CHPL needs most sodium hydroxides
Reach pH curve break, CHPL has strongest alkali resistant ability, because containing most carboxyls and carboxyl tool in CHPL
Standby stronger acidity.However the amount that L and CPL reach the sodium hydroxide consumed at pH knee of curve is less even less than aqueous solution institute
The amount of the sodium hydroxide needed, it may be possible to due to containing some functional groups that can be protonated in lignin, such as hydroxyl and ehter bond
Deng in addition also containing N, S element in lignin, protonation can hold onto hydrogen ion and show lewis base property.CPL ratio L has
Weaker alkali resistant ability, it may be possible to the phenolic hydroxyl group performance introduced into lignin compared with polyphenol hydroxyl and in lignin since phenolate is modified
Alkalinity, CPL also introduce carboxyl, but the alkali resistance that material has not been shown into lignin, and there are two reason possibility: first is that
Carboxymethylated reaction site is insufficient, and the carboxyl amount of introducing is fewer, this point available evidence in infrared spectroscopy；Second is that
Carboxymethylated reaction site is phenolic hydroxyl group, and the carboxyl introduced is made to be more likely to a kind of armaticity carboxyl, and the acidity of performance is not strong.
The reaction site of CHPL carboxymethyl-modification be mostly in methylol position, the carboxyl of introducing by aromatic rings conjugated system influenced compared with
Small, carboxyl is more likely to aliphatic carboxylic acid, acid strong.It is L, Zn from Fig. 92+And L-Zn2+Potentiometric titration curve, Tu10Wei
CPL,Zn2+And CPL-Zn2+Potentiometric titration curve, Figure 11 CHPL, Zn2+And CHPL-Zn2+Potentiometric titration curve, from Fig. 9,
10 and 11 as can be seen that Zn2+Titration curve to have a unexpected inflection point should be Zn2+Precipitating is initially formed at this pH.But
It is L, CPL, CHPL are added in zinc solution, and inflection point becomes gentle, it can be observed how the ability sequence for making inflection point flatten slow from figure
It is CHPL > CPL > L.CPL makes zinc ion solution inflection point flatten slow ability greater than L, and CPL also has compared with L in fig. 8
Weaker alkali resistant ability, the result of such a reversion is strong to be demonstrated between the carboxyl and zinc ion that carboxy methylation introduces
Coordination has released H+。
Zn2+With H+Then competitive binding site promotes ROOH to discharge more H+.Zn in this way2+And ROO–It carries out
Coordination, and from the structure of modified product analysis coordination result chelate structure easy to form, explain CHPL and CPL to zinc from
The large amount of adsorption of son is in the reason of the L.
Modified product is characterized using infrared spectroscopy, elemental analysis, thermogravimetric analysis, show modified-reaction at
Function.
Analysis shows CHPL has best dissolution properties, water dispersible is good for dissolubility and water-dispersible granule.It is unmodified
Lignin (L) has low-down water solubility, and water-soluble component has medium water solubility, water-soluble component lower than 8.7%, CPL
For 34.7%, CHPL there is best water-soluble property water solubility component to account for 69.7%.The sample of CPL and CHPL compared with lignin L
Product have based on small particle size distribution range and fine particle.
Modified sample, which shows CHPL each component all to the adsorption experiment of zinc ion, has big zinc ion adsorbance, and
Consolidated statement reveals best zinc ion adsorption capacity.
Constant-current titration the result shows that, compared with L and CPL CHPL have more carboxyl-contents and strong acidity, also indicate that
CPL and CHPL and Zn2+Coordination Adsorption has occurred, successfully explains CPL and CHPL with stronger adsorption capacity.
Synthesis result shows that modified product CHPL has as a kind of semi-synthetic highly effective chelating agent as water-soluble micro- fertilizer
Very big application potential.
Below using the conditions such as different raw material additive amount, mixing time and reaction temperature preparation phenolate methylolation and carboxylic
Methylated lignin is simultaneously measured its dissolution rate and adsorption capacity, addition amount of sodium hydroxide, mixing time, reaction temperature
Degree, monoxone additional amount, dissolution rate and zinc ion adsorbance are as shown in table 2., from table 2 it can be seen that compared with lignin, phenol
Change methylolation and carboxy methylation lignin dissolution rate and adsorption capacity are preferable.And dissolution rate and absorption under conditions of the 5th group
Effect is best.
The CHPL dissolution rate and adsorption capacity of 2 different parameters of table preparation
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (4)
1. the preparation method of a kind of phenolate methylolation and carboxy methylation lignin, which comprises the steps of:
(1) it prepares phenolate lignin: the lignin of 1 parts by weight being mixed with the phenol of 0.3-4 parts by weight and sulfuric acid is added thereto
Solution obtains mixed liquor, and the concentration of the sulfuric acid is 70%-98%, H in the mixed liquor2SO4Mass fraction be 0.5-
10%；It boils 0.5-4h and obtains the first sediment, first drying precipitate is obtained into the phenolate lignin；
(2) preparation phenolate and hydro methylated lignin: the concentration that the phenolate lignin is dissolved in is the sodium hydroxide of 1-4mol/L
In solution, the formalin that accommodating mass fraction is 30-40% is then added thereto and reacts 0.5-3h；The phenolate wood
The mass volume ratio of element, sodium hydroxide solution and formalin is 1g:3-10mL:3-10ml；Then the hydrochloric acid for being 0-3 with pH value
Solution is acidified 10-60min, and centrifugation obtains the second sediment, and second drying precipitate is obtained the phenolate and hydroxyl
Methylated lignin；
(3) by phenolate and hydro methylated lignin carries out carboxy methylation processing: by the phenolate hydro methylated lignin, isopropanol and
Sodium hydroxide is that 1g:10-60ml:1-4g hybrid reaction 0.5-2h obtains the first reaction solution according to mass volume ratio, will be described
First reaction solution, which is warming up to 40-90 DEG C and chloroacetate reaction 0.5-3h is added thereto, obtains the second reaction solution, the addition
The 1-4:2 of monoxone and phenolate hydro methylated lignin quality；Chloroacetate reaction 0.5-3h is added into second reaction solution to obtain
To third reaction solution, the mass ratio of the monoxone being added into the second reaction solution and phenolate hydro methylated lignin is 1-4:
2；Then the pH value for adjusting third reaction solution is 5-8, removes substance of the molecular weight less than 3500, is drying to obtain the phenolate hydroxyl
Methylate simultaneously carboxy methylation lignin.
2. the preparation method of phenolate methylolation according to claim 1 and carboxy methylation lignin, which is characterized in that described
Substance of the removing molecular weight less than 3500 use dialysis.
3. the preparation method of phenolate methylolation according to claim 2 and carboxy methylation lignin, which is characterized in that described
Drying be lyophilized in freeze drier.
4. a kind of phenolate methylolation and carboxy methylation lignin, which is characterized in that the phenolate methylolation and carboxy methylation
Lignin method as described in claim 1-3 any one is prepared, the phenolate methylolation and carboxy methylation lignin
Water-soluble rate is 50%-90%, and the adsorbance to zinc ion is 90-180mg/g.
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