CN105219393B - The preparation method of lignin modification heavy metal deactivator - Google Patents
The preparation method of lignin modification heavy metal deactivator Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of lignin modification heavy metal deactivator, and this approach includes the following steps：(11) by a certain amount of lignin wiring solution-forming soluble in water, and solution is adjusted to acidity；(2) frerrous chloride and hydrogen peroxide are sequentially added by a certain percentage, and heating is stood after reaction a period of time；(3) adjustment solution is to alkalinity, after sequentially add a certain amount of diethylenetriamine and formaldehyde, stir evenly, and heat reaction a period of time；(4) after reaction under stirring be added dropwise hydrochloric acid solution so that product is fully precipitated, stand, filter after obtain amination modifying lignin；(5) unreacted medicament is washed with water, after by product drying, grinding, that is, obtain lignin amination modifying heavy metal deactivator finished product.The method of the present invention is simple for process, production cost is low, has excellent performance, applied widely, is adapted to the passivation repair process and heavy metal ion-containing waste water absorption, During Coagulation Process of all kinds of heavy metal ion contaminated soils.
Description
Technical field
The present invention relates to heavy metal pollution of soil passivation treatment technology fields, more particularly to a kind of to be changed using lignin amination
Property prepares the preparation method of heavy metal deactivator.
Background technology
As the industries such as mining, smelting, lead accumulator, leather, chemical industry continue to develop, " three wastes " containing heavy metal are by each
Kind approach enters soil environment, and serious pollution is caused to soil.Heavy metal pollution wide, duration with pollution range
The characteristics of growing, polluting concealment, can not be biodegradable not only generates larger harm to the yield and quality of crops, but also
It is constantly enriched with by the transmission of food chain, is finally accumulated in human body and endanger health.According to Chinese Ministry of Environmental Protection, Ministry of Land and Resources in 2014
The national soil investigation bulletin of publication points out that the soil gross contamination of 6,300,000 investigated in China square kilometre is exceeded
Rate is 16.1%, and mainly based on the inorganic pollutions such as cadmium, mercury, arsenic, copper, lead, chromium, zinc, nickel, points of contamination digit accounts for all exceeded
The 82.8% of point.Currently, common heavy metal-polluted soil administering method mainly has peripheral doses, chemical remediation and biology both at home and abroad
Repair three kinds of methods.Peripheral doses method includes soil moved in improve the original displacement, deep ploughs and dig, and chemical repair method includes passivation reparation, soil
Earth elution etc., biological renovation method includes animal reparation, plant extract etc..Wherein, passivation restoration of soil polluted by heavy metal has
Of low cost, the features such as repairing efficiency is short, easy to implement, the item of current China's heavy-metal contaminated soil reparation can be met well
Part requirement is particularly suitable for repairing large area mild or moderate heavy metal pollution agricultural land soil.
Current existing soil heavy metal passivant can be divided into following two categories：(1) inorganic, including lime, sulfuric acid are sub-
Iron, phosphoric acid salt (hydroxyapatite, phosphate fertilizer etc.), industrial by-product category (red mud, flying dust, dolomite residue etc.), clay mineral
Class (zeolite, attapulgite, sepiolite, bentonite etc.) etc.；(2) organic, including organic compost, stalk, municipal sludge, livestock and poultry
Excrement and the chelating type organic matter etc. of synthesis.Wherein, organic passivator has and increases soil fertility and convenient material drawing, economy
The advantages of, have great importance in heavy metal pollution of soil reparation.Studies have shown that lignin and modified product to soil without
Toxic effect, non-secondary pollution.Meanwhile lignin have low biological degradability, and degrade generate humus equally have compared with
Therefore strong heavy metal adsorption has using lignin as Material synthesis soil heavy metal passivant in terms of long-term effect only
Special advantage.In addition, lignin is the main component of pulping and paper-making waste liquid, it is the main source that pulp and paper industry causes environmental pollution
One of head substance, prepares the added value that lignin not only can be improved in soil heavy metal passivant by lignin modification, can also reduce
The pollution of environment, turns waste into wealth.
Ge it is round publication number CN102784622A, application number 201210248082.2 patent of invention in propose with wood
Quality prepares the preparation method of lignin-base dithiocarbamates heavy metal ion agent for capturing, but the capture as raw material
Reaction temperature is higher, the reaction time is longer, step is more needed for agent preparation, less efficient.Meanwhile in the agent for capturing preparation process
High requirement not only is proposed to production technology as raw materials for production using with more supervirulent carbon disulfide, but also can be to life
Production personnel, surrounding enviroment cause damages and risk.Zhao Tao, Pan Hong are in publication number CN103408767A, application number
It proposes to synthesize ring under certain condition as raw material using alkali lignin and epoxychloropropane in the patent of invention of 201310317674.X
Oxygen lignin, and this epoxy lignin derivative is reacted to the preparation method for preparing aminated lignin with polyamine compounds.But it should
Preparation method fails the modified sites of lignin fully exposure, modification efficiency is relatively low, and modifying agent is only with Diamines chemical combination
Object, it is less to the binding site of heavy metal.
Invention content
Technical problem to be solved by the invention is to provide a kind of preparation method of lignin modification heavy metal deactivator, with
Lignin in papermaking wastewater is main component, the new way that comprehensive utilization of only trade waste is not opened up, and can be significantly
Reduce heavy-metal contaminated soil treatment cost.
The present invention solves above-mentioned technical problem with following technical solution：
The preparation method of lignin modification heavy metal deactivator of the present invention, includes the following steps：
The first step weighs a certain amount of lignin and is added to the water the lignin liquor for being made into that mass concentration is 2-10%, stirs
It is 3.5 that solution ph is adjusted after mixing 0.5 hour,
Second step sequentially adds the hydrogen peroxide that frerrous chloride and mass concentration are 30%, quiet after being reacted 1 hour at 50 DEG C
It sets to 0 .5 hours,
Third walks, and adjustment solution ph is 9.5, then sequentially adds diethylenetriamine and formaldehyde, stirs evenly, and heats
It is reacted 1-4 hours to 50-80 DEG C,
4th step, it is that the above-mentioned reaction of 10% hydrochloric acid solution adjusting is molten that mass concentration is added dropwise under stirring after reaction
The pH value of liquid is 7.0, and modified lignin is made fully to be precipitated, and is filtered after standing 2-3 hours, obtains amination modifying lignin,
Unreacted diethylenetriamine and formaldehyde is washed with water in 5th step, after product is dried 6 hours at 50 DEG C, grind
To 100 mesh hereinafter, obtaining lignin amination modifying heavy metal deactivator finished product.
The lignin is to extract from papermaking wastewater, and alkali lignin or lignin sulfonic acid is obtained by filtration by acid adding precipitation
Salt.
Hydrogen peroxide described in preparation process second step is by volume 1 ︰ 200 with lignin liquor, and frerrous chloride adds ratio
Example is according to iron ion and H2O2Mass ratio is 1 ︰ 4-7.
The mass ratio of lignin and diethylenetriamine described in preparation process third step is 1 ︰ 0.75-1.5.
The molar ratio of diethylenetriamine and formaldehyde described in preparation process third step is 1 ︰ 0.5-3.
The method of the present invention has the following advantages that：
1) lignin used is the main component of pulping and paper-making waste liquid, and lignin modification is prepared heavy metal-polluted soil passivation
The added value of lignin not only can be improved in agent, can also reduce the pollution of environment, turn waste into wealth.
2) lignin is carried out diethylenetriamine modification by the present invention, obtains aminated lignin, and synthetic method is simple, reaction
Condition is compared with mild, operability is strong.Heavy metal deactivator obtained is neutrality, non-secondary pollution free of toxic effects to soil, property
Matter is stablized, and has very strong heavy metal adsorption, passivation ability.
3) passivating agent products produced by the invention have wide range of applications, and cannot be only used for heavy metal-polluted soil passivation, also can be used
Make heavy metal in water adsorbent.
Specific implementation mode
The method of the present invention is further described with reference to specific embodiment.
Embodiment 1
The preparation method of lignin modification heavy metal deactivator, operating procedure are as follows：
The first step weighs 4.0g alkali lignins and is added in 200mL distilled water, stirs 0.5 hour, with hydrochloric acid conditioning solution pH
Value to 3.5,
Second step sequentially adds frerrous chloride and 1mL mass concentrations as 30% hydrogen peroxide, and the dosage of frerrous chloride is pressed
m(Fe2+):m(H2O2The ︰ of)=1 4 is added, and 0.5 hour is stood after being reacted 1 hour at 50 DEG C,
Third walks, and adjusts solution ph to 9.5 with NaOH solution, the diethylenetriamine of 5g is added, then press diethylenetriamine
Molar ratio with formaldehyde is 1:0.5 is added 0.024mol formaldehyde, stirs evenly, and solution is kept to be reacted 1 hour at 80 DEG C,
The hydrochloric acid solution that mass concentration is 10% is added dropwise under stirring and adjusts above-mentioned reaction after reaction for 4th step
The pH value of solution is 7.0, and modified lignin is made fully to be precipitated, and is filtered after standing 2 hours, unreacted is washed with deionized water
Diethylenetriamine and formaldehyde, after product is dried 6 hours at 50 DEG C, be ground to 100 mesh hereinafter, i.e. obtain lignin amination change
Property heavy metal deactivator finished product.
The lignin amination modified product nitrogen content of gained is 4.05%.
Embodiment 2
The preparation method of lignin modification heavy metal deactivator, operating procedure are as follows：
The first step weighs 10.0g alkali lignins and is added in 200mL distilled water, stirs 0.5 hour, use hydrochloric acid conditioning solution
PH value to 3.5,
Second step sequentially adds frerrous chloride and 1mL mass concentrations as 30% hydrogen peroxide, and the dosage of frerrous chloride is pressed
m(Fe2+):m(H2O2The ︰ of)=1 6 is added, and 0.5 hour is stood after being reacted 1 hour at 50 DEG C,
Third walks, and solution ph is adjusted to 9.5 with NaOH solution, is added 10g diethylenetriamines, then by diethylenetriamine and
The molar ratio of formaldehyde is 1:3 are added 0.29mol formaldehyde, stir evenly, and solution is kept to be reacted 3 hours at 70 DEG C,
The hydrochloric acid solution that mass concentration is 10% is added dropwise under stirring and adjusts above-mentioned reaction after reaction for 4th step
The pH value of solution is 7.0, and modified lignin is made fully to be precipitated, and is filtered after standing 2 hours, unreacted is washed with deionized water
Diethylenetriamine and formaldehyde, after product is dried 6 hours at 50 DEG C, be ground to 100 mesh hereinafter, i.e. obtain lignin amination change
Property heavy metal deactivator finished product.
The lignin amination modified product nitrogen content of gained is 7.00%.
Embodiment 3
The preparation method of lignin modification heavy metal deactivator, operating procedure are as follows：
The first step weighs 20.0g alkali lignins and is added in 200mL distilled water, stirs 0.5 hour, use hydrochloric acid conditioning solution
PH value to 3.5,
Second step sequentially adds frerrous chloride and 1mL mass concentrations as 30% hydrogen peroxide, and the dosage of frerrous chloride is pressed
m(Fe2+):m(H2O2The ︰ of)=1 7 is added, and 0.5 hour is stood after being reacted 1 hour at 50 DEG C,
Third walks, and solution ph is adjusted to 9.5 with NaOH solution, is added 15g diethylenetriamines, then by diethylenetriamine and
The molar ratio of formaldehyde is 1:2 are added 0.29mol formaldehyde, stir evenly, and solution is kept to be reacted 4 hours at 50 DEG C,
The hydrochloric acid solution that mass concentration is 10% is added dropwise under stirring and adjusts above-mentioned reaction after reaction for 4th step
The pH value of solution is 7.0, and modified lignin is made fully to be precipitated, and is filtered after standing 3 hours, unreacted is washed with deionized water
Diethylenetriamine and formaldehyde, after product is dried 6 hours at 50 DEG C, be ground to 100 mesh hereinafter, i.e. obtain lignin amination change
Property heavy metal deactivator finished product.
The lignin amination modified product nitrogen content of gained is 5.34%.
Embodiment 4
The preparation method of lignin modification heavy metal deactivator, steps are as follows：
The first step weighs 16.0g sodium lignin sulfonates and is added in 200mL distilled water, stirs 0.5 hour, adjusted with hydrochloric acid
Solution ph to 3.5,
Second step sequentially adds frerrous chloride and 1mL mass concentrations as 30% hydrogen peroxide, and the dosage of frerrous chloride is pressed
m(Fe2+):m(H2O2)=1:5 are added, and 0.5 hour is stood after being reacted 1 hour at 50 DEG C,
Third walks, and solution ph is adjusted to 9.5 with NaOH solution, is added 24g diethylenetriamines, then by diethylenetriamine and
The molar ratio of formaldehyde is that 0.23mol formaldehyde is added in 1 ︰ 1, is stirred evenly, and solution is kept to be reacted 2 hours at 60 DEG C,
The hydrochloric acid solution that mass concentration is 10% is added dropwise under stirring and adjusts above-mentioned reaction after reaction for 4th step
The pH value of solution is 7.0, and modified lignin is made fully to be precipitated, and is filtered after standing 2 hours, unreacted is washed with deionized water
Diethylenetriamine and formaldehyde, after product is dried 6 hours at 50 DEG C, be ground to 100 mesh hereinafter, i.e. obtain lignin amination change
Property heavy metal deactivator finished product.
The lignin amination modified product nitrogen content of gained is 3.88%.
Test example 1
It is commented with heavy metal amount of capacity in lignin amination modifying heavy metal deactivator finished product adsorption aqueous solution of the present invention
Sentence modified product heavy metal passivation ability.Amination modifying heavy metal deactivator finished product is to Cu in solution in embodiment 12+、Pb2+、Cd2 +、Zn2+Saturated extent of adsorption be respectively 10.48mg/g, 58.91mg/g, 25.13mg/g, 16.17mg/g.Amination in embodiment 2
Modified heavy metal deactivator finished product is to Cu in solution2+、Pb2+、Cd2+、Zn2+Saturated extent of adsorption be respectively 23.73mg/g,
76.62mg/g,31.69mg/g,21.85mg/g.Amination modifying heavy metal deactivator finished product is to Cu in solution in embodiment 32+、
Pb2+、Cd2+、Zn2+Saturated extent of adsorption be respectively 12.40mg/g, 15.12mg/g, 19.52mg/g, 14.64mg/g.Implement
Amination modifying heavy metal deactivator finished product is to Cu in solution in example 42+、Pb2+、Cd2+、Zn2+Saturated extent of adsorption be respectively
12.365mg/g,18.84mg/g,10.70mg/g,5.71mg/g.Comparison Zhou Yan exists《Environmental project journal》In October, 2013 is sent out
Table《Absorption of the aminated lignin to Cu in water (II), Cd (II)》Aminated lignin is to Cu in text2+、Cd2+Adsorption capacity
6.2mg/g and 7.1mg/g has significant advantage.
Test example 2
Cultivate to obtain analog composite heavy-metal contaminated soil, heavy metal concentration is cadmium 21.51mg/g, lead 1968.85mg/g,
Zinc 2175.63mg/g, copper 1353.43mg/g.It takes 10g to air-dry simulation heavy-metal contaminated soil sample and is placed in the clean burnings of 250mL
In cup, the dosage of lignin amination modifying heavy metal deactivator finished product of the present invention is soil quality 5%, it is ensured that soil it is aqueous
Rate is 30%, is stirred evenly, and is conserved 14 days.After 14 days, the soil after repairing is taken, using the toxicity leaching side of HJ/299-2007
The Acid extractable of method and BCR methods determines the effect of passivator.Cadmium concentration after addition passivator in toxicity leachate reduces
47.40%, lead concentration, which reduces by 79.31%, zinc concentration and reduces by 62.36%, copper concentration, reduces by 95.90%, in Acid extractable
Cadmium concentration, which reduces by 3.97%, lead concentration, which reduces by 19.51%, zinc concentration, reduces by 23.60%, copper concentration reduction by 28.76%.
Claims (2)
1. the preparation method of lignin modification heavy metal deactivator, which is characterized in that include the following steps：
The first step weighs a certain amount of lignin and is added to the water the lignin liquor for being made into that mass concentration is 2-10%, stirring 0.5
It is 3.5 that solution ph is adjusted after hour；
Second step sequentially adds frerrous chloride and mass concentration as 30% hydrogen peroxide, is stood after being reacted 1 hour at 50 DEG C
0.5 hour, hydrogen peroxide described in second step was by volume 1 ︰ 200 with lignin liquor, and frerrous chloride adds ratio according to iron
Ion and H2O2Mass ratio is 1 ︰ 4-7；
Third walks, and adjustment solution ph is 9.5, then sequentially adds diethylenetriamine and formaldehyde, stirs evenly, and is heated to
50-80 DEG C is reacted 1-4 hours, and the mass ratio of lignin and the diethylenetriamine is 1 ︰ 0.75-1.5, third step in third step
Described in the molar ratio of diethylenetriamine and formaldehyde be 1 ︰ 0.5-3；
4th step, it is that 10% hydrochloric acid solution adjusts above-mentioned reaction solution that mass concentration is added dropwise under stirring after reaction
PH value is 7.0, and modified lignin is made fully to be precipitated, and is filtered after standing 2-3 hours, obtains amination modifying lignin；
Unreacted diethylenetriamine and formaldehyde is washed with water in 5th step, after product is dried 6 hours at 50 DEG C, be ground to 100
Mesh is hereinafter, obtain lignin amination modifying heavy metal deactivator finished product.
2. the preparation method of lignin modification heavy metal deactivator according to claim 1, it is characterised in that：It is described wooden
Element is to extract from papermaking wastewater, and the alkali lignin or lignosulfonates that are obtained by filtration are precipitated by acid adding.
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