CN108585101A - A kind of recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization - Google Patents

A kind of recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization Download PDF

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CN108585101A
CN108585101A CN201810376372.2A CN201810376372A CN108585101A CN 108585101 A CN108585101 A CN 108585101A CN 201810376372 A CN201810376372 A CN 201810376372A CN 108585101 A CN108585101 A CN 108585101A
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inorganic material
hectorite
biological matter
multiporous biological
microballoon
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CN108585101B (en
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卢伟
王瑞峰
孙蓓蓓
隋永祥
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Xinyi Xiyi High Tech Material Industry Technology Research Institute Co Ltd
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3441Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/345Regenerating or reactivating using a particular desorbing compound or mixture
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46Materials comprising a mixture of inorganic and organic materials
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Abstract

The invention belongs to biomass technical fields, and in particular to a kind of multiporous biological matter microballoon and preparation method thereof of heavy metal-polluted water process inorganic material hydridization.The present invention is combined using to be modified sorghum stalk and modified hectorite as raw material the multiporous biological matter microballoon of inorganic material hydridization;The adsorbable heavy metal ions in wastewater of composite material and aniline prepared, phenol organic pollution, Pyrogentisinic Acid's eliminating rate of absorption are up to 99%.

Description

A kind of multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization returns Receiving method
Original bill application number 2017110184467, title a kind of heavy metal-polluted water process multiporous biological matter microballoon and its system Preparation Method, applying date 2017.10.27.
Technical field
The invention belongs to biomass technical fields, and in particular to a kind of heavy metal-polluted water process inorganic material hydridization it is more The recovery method of hole biomass microballoon.
Background technology
With the continuous development of industrial development process, China's soil makes by serious pollution, wherein heavy metal pollution The main Types of soil pollution, major pollutants type are chromium(Cd), nickel(Ni), copper(Cu), mercury(Hg), lead(Pb)Deng.At present China's arable soil heavy metals exceeding standard point is mainly based on middle low heavy metal pollution, therefore, to realize that agricultural is normal raw The double goal of production and heavy metal-polluted soil reparation, we usually add modifying agent in the soil(It is commonly called as passivator)By heavy metal to Low dissolving, fixed, less toxic Forms Transformation reduce enrichment of the heavy metal in plant body, reach and ensure the same of agricultural production When, reduce the purpose of polluted heavy metals environmental risk.
Currently, widely used soil passivation renovation agent includes mainly inorganic passivant and organic passivation agent two major classes;Its Middle phosphate compound such as hydroxyapatite(Hydroxyapatite, abbreviation HAP)It is the relatively broad passivation of current application Renovation agent.Hu Tiantian(Repairing research [D] Anhui agriculture of the Hu Tiantian nanometer hydroxyapatites to heavy metal copper and lead-contaminated soil Sparetime university is learned, and 2012)Exchangeable species and carbonate knot in soil can effectively be reduced by verifying micron order HAP by cell field trial The content for closing state Cu reduces the Ecological Environment Risk of Cu.
Agricultural University Of South China discloses a kind of biomass carbon heavy metal-polluted soil renovation agent(CN 105622290 A), with chicken manure Or oil tea shell is preferable to the Cu adsorptivities in soil by biomass carbon obtained by 450-550 DEG C of high-temperature calcination, but adsorb heavy metal Element is more single;The method that a kind of composite biomass absorption heavy metal is reported in 102583619 A of CN, with Chinese chestnut pericarp, Rice aerial part biomass, cattail aerial part biomass are that raw material forms composite biomass, can be water-soluble by Adsorption Various heavy in liquid.Dalian University of Technology Ma Wei et al.(CN 103316640 B)Have developed a kind of magnetic green substance suction Attached dose is removed removing heavy metals, and mixing is crushed as raw material using wood powder, shell, corn stalk biomass, then uses the chitosan of acetic acid Solution mixes, and magnetisable material is added, and by lye cure obtaining the magnetic biomass adsorbent of tool, but also only has studied pair As(V)Adsorption capacity, so adsorptivity is single.
Invention content
The object of the present invention is to provide a kind of biological material of novel inorganic hydridization, the present invention is to be modified sorghum stalk and change Property hectorite be that raw material is combined the multiporous biological matter microballoon of inorganic material hydridization;The adsorbable waste water of composite material prepared Middle heavy metal ion and aniline, phenol organic pollution, Pyrogentisinic Acid's eliminating rate of absorption are up to 99%.
According to an aspect of the present invention, the present invention provides a kind of multiporous biological matter microballoon of inorganic material hydridization, institutes Multiporous biological matter microballoon is stated to be formed with hectorite hydridization by sorghum stalk;
The preparation method of the multiporous biological matter microballoon of inorganic material hydridization of the present invention is as follows:
1)The modification of sorghum stalk:
A) pulverizing process:It is that 200 mesh or less obtain sorghum stalk biological particles that grain size is crushed to after sorghum stalk is dried;
B) soda acid treatment process:100g sorghums stalk biological particles are placed in stirring dipping 30min in 3wt% phosphate aqueous solutions, so It is placed in the potassium hydroxide aqueous solution of 5wt% and impregnates 10min at 50 DEG C, filtering, originally water washing to filtrate are at sourly neutral The biological particles of alkali modification;Phosphate aqueous solution and potassium hydroxide aqueous solution dosage are can submerge sorghum stalk biological particles Preferably;
C) oxidation operation:The biological particles that soda acid is modified are placed in oxidation processes in the potassium permanganate solution of a concentration of 5wt% 1-2h obtains oxidizing biomass dispersion liquid;Contain a large amount of cellulose and hemicellulose in biomass, takes potassium permanganate can be with oxygen Change forms exposed carboxyl;
D) grafting reacts:Then it is added at 40 DEG C of N- (tertbutyloxycarbonyl) amion acetic acids and the concentrated sulfuric acid and reacts 2h, then 70 DEG C Lower reaction 2h;Filter, be washed to filtrate at it is neutral, dry amion acetic acid grafting biomass;Amion acetic acid is in the concentrated sulfuric acid Under the action of with the exposed carboxyl formed in oxidation operation form acid anhydrides, while slough protecting group expose amino and sulfuric acid at Salt;
2)The preparation of composite modified hectorite:
(1)Hectorite quaternization:It is that 200 mesh hectorite below is placed in stearyl dimethyl benzyl ammonium chloride by granularity Ultrasonic disperse 48h obtains the hectorite dispersion liquid of quaternization in aqueous solution;Every gram of hectorite needs 0.12-0.20g octadecyls Dimethyl benzyl ammonium chloride;
(2)The complexing of hectorite:Ethylenediamine is added into hectorite dispersion liquid to be complexed, 12h is stirred at 40 DEG C, is then filtered It is detected to filtrate without chlorion with silver nitrate;Composite modified hectorite is dried to obtain at 70 DEG C;Every gram of hectorite needs 0.05- 0.10g ethylenediamines;Ethylenediamine is loaded on the hectorite of quaternization by being complexed in the step process;
3)The preparation of the multiporous biological matter microballoon of inorganic material hydridization:
The biomass of the composite modified hectorites of 10g and 8g amion acetic acid graftings is placed in the aqueous solution of 100ml ethyl alcohol and is stirred Uniformly, 0.1g triethylamines are added, are filtered after crosslinking agent glutaraldehyde back flow reaction 2h then is added, wash, dry inorganic material The multiporous biological matter microballoon of hydridization.It is in order to by amino in the biomass of amion acetic acid grafting that triethylamine is added in the present invention Sulfate, which dissociates, to be come, compound to make amino in biomass, the amino sites of hectorite load and glutaraldehyde cross-linking be formed Material;
Preferably, oxidation temperature is 10-20 DEG C in the oxidation operation, and the dosage of potassium permanganate is that sorghum obstructs biomass 0.08-0.13 times of grain weight;Contain a large amount of cellulose and hemicellulose in sorghum stalk, is to give birth in oxidation operation The carbon-carbon bond oxidation scission of cellulose and hemicellulose in substance forms part carboxyl;Generally selecting property of potassium permanganate is low, oxidation Temperature directly determines the degree of follow-up grafting reaction, and then influence the multiporous biological matter microballoon of final inorganic material hydridization Pattern and its physicochemical property;
Preferably, the dosage of N- (tertbutyloxycarbonyl) amion acetic acid is that sorghum obstructs biological particles weight in the grafting reaction 0.21-0.32 times;
Preferably, the dosage of the crosslinking agent glutaraldehyde is 0.3-0.5g;
Preferably, drying temperature is 65 DEG C in the preparation process of the multiporous biological matter microballoon of the inorganic material hydridization, specific surface Product reaches 79.2m2.g-1;It is found in research, the drying temperature in the preparation process of the multiporous biological matter microballoon of inorganic material hydridization The specific surface area that can influence multiporous biological matter microballoon, when naturally dry at 20-30 DEG C, specific surface area is smaller, and 70 DEG C or more porous Biomass structure in biomass microballoon, which gradually collapses, causes the aperture of microballoon to become larger, and is all unfavorable for heavy metal or organic dirt Contaminate the absorption of object.
According to another aspect of the invention, the present invention provides a kind of use of the multiporous biological matter microballoon of inorganic material hydridization On the way, for adsorbing heavy metal ion, phenol and aniline in waste water in the environment of certain pH value;The heavy metal is Pb2+、 Cr2+、Cu2+、Ni2+Or Zn2+;The multiporous biological matter microballoon of inorganic material hydridization prepared by the present invention has nitrogen oxygen electron rich group, The binding site of absorption can be provided with heavy metal ion, in addition can adsorb organic pollution by hydrogen bond and porous structure.
The purposes of the multiporous biological matter microballoon of a kind of inorganic material hydridization according to the present invention, in the ring of certain pH value For adsorbing heavy metal ion, phenol and aniline in waste water under border;The heavy metal is Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+; In the environment of different pH, the multiporous biological matter microballoon of inorganic material hydridization to heavy metal, aniline, phenol adsorption effect not Together, Pb is adsorbed2+、Cr2+、Cu2+、Ni2+Or Zn2+PH environment be respectively:Pb2+For 4.3-5.2, Cr2+For 5.2-5.5, Cu2+For 6.2-6.5, Ni2+For 4.3-4.8;Zn2+For 3.2-7.8;The pH environment of adsorbing phenol is 5.5-6.4, the pH environment of adsorption of aniline For 7.8-8.2.
It, can be molten by hydrochloric acid after the multiporous biological matter microballoon of inorganic material hydridization prepared by the present invention is used to adsorb heavy metal Liquid desorbs the heavy metal that it is adsorbed, and the multiporous biological matter microballoon of the inorganic material hydridization after desorption is activated by being heat-treated It repeats and utilizes afterwards.
Compared with prior art, the invention has the advantages that:
1)It is combined the new of inorganic material hydridization as raw material the present invention provides a kind of using being modified sorghum stalk and modified hectorite Type multiporous biological matter microballoon, the novel porous biomass microballoon have excellent specific surface area, reach 79.2m2.g-1
2)Multiporous biological matter microballoon prepared by the present invention can be used for adsorbing contents of many kinds of heavy metal ion, and can simultaneously adsorption of aniline and/ Or phenol;
3)The heavy metal of the multiporous biological matter microballoon absorption prepared through the invention can carry out the solution of heavy metal by hydrochloric acid solution It inhales, acidolysis repeats to utilize after inhaling by the multiporous biological matter microballoon of heat treatment adsorbs heavy metal again.
Description of the drawings
Fig. 1 is the multiporous biological matter microballoon electron-microscope scanning figure of inorganic material hydridization prepared by the present invention.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
Prepare the multiporous biological matter microballoon of inorganic material hydridization:
1)The modification of sorghum stalk:
A) pulverizing process:It is that 200 mesh or less obtain sorghum stalk biological particles that grain size is crushed to after sorghum stalk is dried;
B) soda acid treatment process:100g sorghums stalk biological particles are placed in 200ml 3wt% phosphate aqueous solutions and stir dipping 30min is subsequently placed in the potassium hydroxide aqueous solution of 200ml 5wt% and impregnates 10min at 50 DEG C, and filtering, originally water washing are extremely Filtrate is at the neutral biological particles for obtaining soda acid and being modified;
C) oxidation operation:The biological particles that soda acid is modified are placed in the potassium permanganate solution of a concentration of 5wt% in 10-20 Oxidation processes 1-2h obtains oxidizing biomass dispersion liquid at DEG C;The dosage of potassium permanganate is that sorghum obstructs the 0.10 of biological particles weight Times;
D) grafting reacts:Then it is added at 40 DEG C of N- (tertbutyloxycarbonyl) amion acetic acids and the concentrated sulfuric acid and reacts 2h, then 70 DEG C Lower reaction 2h;Filter, be washed to filtrate at it is neutral, dry amion acetic acid grafting biomass;N- (uncles in grafting reaction Butoxy carbonyl) dosage of amion acetic acid is that sorghum obstructs 0.26 times of biological particles weight;
2)The preparation of composite modified hectorite:
(1)Hectorite quaternization:It is that 200 mesh hectorite below is placed in octadecyl dimethyl benzyl chlorination by 100g granularities Ammonium(Every gram of hectorite needs 0.12-0.20g stearyl dimethyl benzyl ammonium chlorides, this embodiment dosage is(Every gram of hectorite Need 0.15g stearyl dimethyl benzyl ammonium chlorides)Aqueous solution in ultrasonic disperse 48h obtain quaternization hectorite dispersion Liquid;
(2)The complexing of hectorite:Ethylenediamine is added into hectorite dispersion liquid(With step 1)Middle hectorite is calculating basis, often Gram hectorite needs 0.05-0.10g ethylenediamines, this embodiment dosage is that every gram of hectorite needs 0.08g ethylenediamines)Carry out network It closes, stirs 12h at 40 DEG C, then filter to filtrate and detected without chlorion with silver nitrate, composite modified water brightness is dried to obtain at 70 DEG C Stone;
3)The preparation of the multiporous biological matter microballoon of inorganic material hydridization:
The biomass of the composite modified hectorites of 10g and 8g amion acetic acid graftings is placed in the aqueous solution of 100ml ethyl alcohol and is stirred Uniformly, 0.1g triethylamines are added, crosslinking agent glutaraldehyde is then added(0.4g)It filters, washes after back flow reaction 2h, done at 65 DEG C The dry multiporous biological matter microballoon that inorganic material hydridization is obtained to constant weight.
Influence of the different drying temperatures of embodiment 2 to multiporous biological matter microballoon specific surface area
(a)Compared with Example 1, difference lies in drying temperatures in the preparation process of the multiporous biological matter microballoon of inorganic material hydridization It it is 20-30 DEG C, remaining preparation process and raw material proportioning are identical with embodiment 1;
(b)Compared with Example 1, difference lies in drying temperatures in the preparation process of the multiporous biological matter microballoon of inorganic material hydridization It it is 80-90 DEG C, remaining preparation process and raw material proportioning are identical with embodiment 1.
Embodiment 3
Heavy metal in the multiporous biological matter microballoon adsorption aqueous solution of inorganic material hydridization is taken, the specific method is as follows, prepares respectively Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+Chloride aqueous solution, molar concentration is 60mmol/L;In addition aniline is prepared respectively With the aqueous solution of phenol, molar concentration is also 60mmol/L;It is micro- with the multiporous biological matter of the inorganic material hydridization of the preparation of embodiment 1 Ball is adsorbent(1.0g adsorbents are added per aqueous solution), heavy metal or organic matter are positioned at 20-30 DEG C of room temperature(Benzene Amine or phenol)Aqueous solution in, using hydrochloric acid or sodium hydroxide regulation system pH to certain section, be then stirred absorption 2h, filtering measure weight in filtrate using the concentration in aniline and phenol in UV detector filtrates tested using Atomic absorption The concentration of metal ion calculates absorption efficiency;As a result as shown in table 1 below:
1 multiporous biological matter microballoon of table adsorbs the adsorption capacity of heavy metal and organic pollution
Note:1) the above removal efficiency is the average value of three points in pH value section, respectively the two of the sections pH endpoint value and One median;Example 2.0-3.0, i.e. pH are respectively 2.0 ± 0.1,2.5 ± 0.1 and 3.0 ± 0.1, and three point values correspond to absorption The average value of efficiency;2)Phenol+Cr2+System represents phenol and CrCl2Mixed solution, the two concentration is 60mmol/L, inhale Attached dose of dosage is similarly every aqueous solution and 1.0g adsorbents is added, and adsorption temp is also 20-30 DEG C, adsorption time 2h.
According in embodiment 2(a)With(b)Multiporous biological matter microballoon prepared by middle preparation method, adsorption test is carried out to it It tests (experimental condition is same as above, i.e. temperature, adsorbent amount, initial concentration etc.), the results are shown in Table 2:
Influence of the different drying temperatures of table 2 to adsorbent absorption property
Since heavy metal can be desorbed with adsorbent under acid condition, so the present invention is attempted according to this principle by adsorbent The desorption of heavy metal is carried out after use, the specific method is as follows:After the multiporous biological matter microballoon of inorganic material hydridization is recovered by filtration It is placed in the aqueous hydrochloric acid solution of 2mol/L the progress ultrasound 2h at 50 DEG C, measures Pb2+、Cr2+、Cu2+、Ni2+Or Zn2+Heavy metal from The desorption rate of son, and constant weight will be dried under vacuum at 50 DEG C of adsorbent after desorption, and it is more than 90% adsorbent weight to desorption rate Adsorption rate after multiple its recycling using test(Test method is same as above), the results are shown in Table 3:
Absorption property after the desorption rate and its recovery of 3 adsorbent of table in acid condition
Note:" --- " indicates not carry out adsorption rate test, wherein Cu since desorption efficiency is too low2+PH environment is adsorbed when recovery It is 7.0;Ni2+It is 4.5 that pH environment is adsorbed when recovery.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.

Claims (2)

1. a kind of Cu2+The recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization, feature exist In:By the multiporous biological matter microballoon of inorganic material hydridization be recovered by filtration in the aqueous hydrochloric acid solution for be placed on 2mol/L at 50 DEG C into Row ultrasound 2h, measures Cu2+The desorption rate of heavy metal ion, and must be returned constant weight is dried under vacuum at 50 DEG C of adsorbent after desorption The multiporous biological matter microballoon of the inorganic material hydridization of receipts;
The multiporous biological matter microballoon of the inorganic material hydridization of the recycling can be used for Adsorption of Cu in the environment of pH environment is 7.02+ Waste water;
The multiporous biological matter microballoon of the inorganic material hydridization is prepared by following preparation method:
1)The modification of sorghum stalk:
A) pulverizing process:It is that 200 mesh or less obtain sorghum stalk biological particles that grain size is crushed to after sorghum stalk is dried;
B) soda acid treatment process:100g sorghums stalk biological particles are placed in 200ml 3wt% phosphate aqueous solutions and stir dipping 30min is subsequently placed in the potassium hydroxide aqueous solution of 200ml 5wt% and impregnates 10min at 50 DEG C, and filtering, originally water washing are extremely Filtrate is at the neutral biological particles for obtaining soda acid and being modified;
C) oxidation operation:The biological particles that soda acid is modified are placed in the potassium permanganate solution of a concentration of 5wt% in 10-20 Oxidation processes 1-2h obtains oxidizing biomass dispersion liquid at DEG C;The dosage of potassium permanganate is that sorghum obstructs the 0.10 of biological particles weight Times;
D) grafting reacts:Then it is added at 40 DEG C of N- (tertbutyloxycarbonyl) amion acetic acids and the concentrated sulfuric acid and reacts 2h, then 70 DEG C Lower reaction 2h;Filter, be washed to filtrate at it is neutral, dry amion acetic acid grafting biomass;N- (uncles in grafting reaction Butoxy carbonyl) dosage of amion acetic acid is that sorghum obstructs 0.26 times of biological particles weight;
2)The preparation of composite modified hectorite:
(1)Hectorite quaternization:It is that 200 mesh hectorite below is placed in octadecyl dimethyl benzyl chlorination by 100g granularities Ultrasonic disperse 48h obtains the hectorite dispersion liquid of quaternization in the aqueous solution of ammonium;Every gram of hectorite needs 0.15g octadecyls two Methylbenzyl ammonium chloride;
(2)The complexing of hectorite:Ethylenediamine is added into hectorite dispersion liquid, every gram of hectorite needs 0.08g ethylenediamines to carry out Complexing stirs 12h at 40 DEG C, then filters to filtrate and is detected without chlorion with silver nitrate, composite modified water is dried to obtain at 70 DEG C Pyroxene;
(3)The preparation of the multiporous biological matter microballoon of inorganic material hydridization:
The biomass of the composite modified hectorites of 10g and 8g amion acetic acid graftings is placed in the aqueous solution of 100ml ethyl alcohol and is stirred Uniformly, 0.1g triethylamines are added, are filtered after crosslinking agent glutaraldehyde 0.4g back flow reactions 2h then is added, wash, it is dry at 65 DEG C The multiporous biological matter microballoon of inorganic material hydridization is obtained to constant weight.
2. a kind of Ni2+The recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization, feature exist In:By the multiporous biological matter microballoon of inorganic material hydridization be recovered by filtration in the aqueous hydrochloric acid solution for be placed on 2mol/L at 50 DEG C into Row ultrasound 2h, measures Ni2+The desorption rate of heavy metal ion, and must be returned constant weight is dried under vacuum at 50 DEG C of adsorbent after desorption The multiporous biological matter microballoon of the inorganic material hydridization of receipts;
The multiporous biological matter microballoon of the inorganic material hydridization of the recycling can be used for adsorbing Ni in the environment of pH is 4.52+Waste water;
The multiporous biological matter microballoon of the inorganic material hydridization is prepared by following preparation method:
1)The modification of sorghum stalk:
A) pulverizing process:It is that 200 mesh or less obtain sorghum stalk biological particles that grain size is crushed to after sorghum stalk is dried;
B) soda acid treatment process:100g sorghums stalk biological particles are placed in 200ml 3wt% phosphate aqueous solutions and stir dipping 30min is subsequently placed in the potassium hydroxide aqueous solution of 200ml 5wt% and impregnates 10min at 50 DEG C, and filtering, originally water washing are extremely Filtrate is at the neutral biological particles for obtaining soda acid and being modified;
C) oxidation operation:The biological particles that soda acid is modified are placed in the potassium permanganate solution of a concentration of 5wt% in 10-20 Oxidation processes 1-2h obtains oxidizing biomass dispersion liquid at DEG C;The dosage of potassium permanganate is that sorghum obstructs the 0.10 of biological particles weight Times;
D) grafting reacts:Then it is added at 40 DEG C of N- (tertbutyloxycarbonyl) amion acetic acids and the concentrated sulfuric acid and reacts 2h, then 70 DEG C Lower reaction 2h;Filter, be washed to filtrate at it is neutral, dry amion acetic acid grafting biomass;N- (uncles in grafting reaction Butoxy carbonyl) dosage of amion acetic acid is that sorghum obstructs 0.26 times of biological particles weight;
2)The preparation of composite modified hectorite:
(1)Hectorite quaternization:It is that 200 mesh hectorite below is placed in octadecyl dimethyl benzyl chlorination by 100g granularities Ultrasonic disperse 48h obtains the hectorite dispersion liquid of quaternization in the aqueous solution of ammonium;Every gram of hectorite needs 0.15g octadecyls two Methylbenzyl ammonium chloride;
(2)The complexing of hectorite:Ethylenediamine is added into hectorite dispersion liquid, every gram of hectorite needs 0.08g ethylenediamines to carry out Complexing stirs 12h at 40 DEG C, then filters to filtrate and is detected without chlorion with silver nitrate, composite modified water is dried to obtain at 70 DEG C Pyroxene;
(3)The preparation of the multiporous biological matter microballoon of inorganic material hydridization:
The biomass of the composite modified hectorites of 10g and 8g amion acetic acid graftings is placed in the aqueous solution of 100ml ethyl alcohol and is stirred Uniformly, 0.1g triethylamines are added, are filtered after crosslinking agent glutaraldehyde 0.4g back flow reactions 2h then is added, wash, it is dry at 65 DEG C The multiporous biological matter microballoon of inorganic material hydridization is obtained to constant weight.
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