CN106492765A - A kind of preparation method of quaternary ammonium salt/oxide modifying biology hybrid material - Google Patents
A kind of preparation method of quaternary ammonium salt/oxide modifying biology hybrid material Download PDFInfo
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- CN106492765A CN106492765A CN201611004077.1A CN201611004077A CN106492765A CN 106492765 A CN106492765 A CN 106492765A CN 201611004077 A CN201611004077 A CN 201611004077A CN 106492765 A CN106492765 A CN 106492765A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/106—Selenium compounds
Abstract
The invention discloses a kind of quaternary ammonium salt/preparation method of oxide modifying biology hybrid material, present invention biology hybrid material adopted 3 chlorine, 2 Hydroxyproyl Trimethyl ammonium chloride to be modified for etherifying agent, prepares cellulose anion etherate with stalk as raw material；Then in its area load metal oxide, quaternary ammonium salt/oxide modifying biology hybrid material is obtained final product；Wherein metal oxide is iron oxide, lanthana or zirconium oxide.The present invention is nontoxic using materials safety, and synthesis technique is simple, environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of the biological hybrid material that is modified with quaternary ammonium salt and nano-oxide, can apply
In multiple process containing the anionic pollutant waste water such as arsenic, selenium, phosphorus, belong to wastewater treatment and agricultural resources utilize field.
Background technology
Arsenic and selenium are typical poisonous and harmful elements, there is extremely strong toxicity, phosphorus then to draw biology including people
One of key reason of body eutrophication is played, is also a kind of non-renewable precious mineral resources.Therefore, no matter at home also
It is that the content of arsenic in water body, selenium and phosphorus has strict restriction in the world.Additionally, China is large agricultural country, produce every year several hundred million
Ton stalk, carries out improper disposal to which（Such as burn etc.）Have resulted in serious atmosphere pollution.Therefore, the resource of agricultural waste material
Change utilization becomes one of environmental problem of greatest concern, while realizing deep treatment and the reality of the pollution of arsenic in water body, selenium and phosphorus
The recycling of existing biomass straw is significant.
Containing abundant cellulose, hemicellulose and lignin in stalk, live with reaction containing substantial amounts of in the structure
The oh group of property, beneficial to carrying out surface modification.Studied using discarded agricultural crop straw at present as raw material, by band
The quaternary ammonium group of positive charge is modified in stalk channel surfaces, on this basis again by metal oxide（Lanthana）It is supported on modified straw
On stalk, the quaternary ammonium salt/oxide modifying biology hybrid material to anionic pollutant with high selectivity is prepared（CN
105214629 A）.But to stalk aminated modified during, employ N, N- dimethylformamides, epoxy chloropropionate
Multiple toxic chemical raw materials such as alkane, ethylenediamine, trimethylamine/triethylamine/urea, synthesis technique is complicated and produces harmful by-products,
Secondary pollution is serious.
Content of the invention
The invention aims to solving defect present in prior art, there is provided a kind of materials safety is nontoxic, synthesis
The quaternary ammonium salt of process is simple and environmental protection/oxide modifying biology hybrid material preparation method.
In order to achieve the above object, the invention provides a kind of preparation of quaternary ammonium salt/oxide modifying biology hybrid material
Method, present invention biology hybrid material adopt the chloro- 2- Hydroxyproyl Trimethyls ammonium chlorides of 3- to carry out for etherifying agent with stalk as raw material
Modification, prepares cellulose anion etherate；Then in its area load metal oxide, quaternary ammonium salt/oxide is obtained final product
Modification biological hybrid material；Wherein metal oxide is iron oxide, lanthana or zirconium oxide.
Metal oxide supported employing in situ deposition method.
Wherein, metal oxide is nano-oxide particles；Which is immobilized in biological exchange by the method for in-situ deposition
Agent surface, is obtained quaternary ammonium salt/oxide modifying biology hybrid material, and load capacity counts percentage by weight as 2-31% with iron, in terms of lanthanum
Percentage by weight is 1-24%, counts percentage by weight as 1-27% with zirconium.
The concrete preparation method of quaternary ammonium salt of the present invention/oxide modifying biology hybrid material is as follows：
（1）Mono- steps of CTA are modified：2-30g agricultural crop straws particle is taken with 20-600mL methanol/isopropanols/ethanol and NaOH water
Solution（Volumetric concentration is 1-50%）Mixed solvent（Volume ratio is 0.1：1-10：1）Mixing, then temperature programming is to 50-120
℃.Then by chloro- for 10-150mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）Uniformly dropped to the speed of 2-60mL/min
In mixed liquor, stirring reaction 0.5-8 hour at 50-120 DEG C.Product is washed to neutrality, 25-80 DEG C of vacuum drying 2- after filtration
24 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Metal oxide supported：Weigh the above-mentioned biological exchangers of 1-20g add 2-100g iron/lanthanum chlorate or nitrate,
Or zirconium oxychloride and 10-500mL HCl（0.1-1mol/L）In mixed solution, 25-80 DEG C of stirring reaction 1-12 hour.By material
Leached with filter screen and be added in 10-500mL NaOH (2-30wt%) solution, 25-80 DEG C of stirring reaction 1-12 hour.After end
Product is washed to neutrality, is then washed with 5-30wt% NaCl solutions, deionized water, 25-80 DEG C of vacuum drying 2-24 hour,
Quaternary ammonium salt/oxide modifying biology hybrid material is obtained.
Wherein, agricultural crop straw includes wheat stalk, rice straw, cotton stalk, maize straw, soybean stalk, cassava
Stalk or its mixture, preferably wheat stalk, rice straw, maize straw, cotton stalk.Average grain diameter is between 0.2-
1.5mm between.
Preferably, in mono- step modifying process of CTA, organic solvent used is isopropanol.
When iron oxide is loaded, the load capacity preferably 18% of iron, with 5g biology exchangers（Prepared using wheat stalk）Add
30g FeCl3·6H2Prepared by O in-situ depositions.
When lanthana is loaded, the load capacity preferably 15% of lanthanum, with 4g biology exchangers（Prepared using rice straw）Add
38 g La(NO3)3·6H2Prepared by O in-situ depositions.
When zirconium oxide is loaded, the load capacity preferably 19% of zirconium, with 6g biology exchangers（Prepared using maize straw）Add
45g ZrOCl2·8H2Prepared by O in-situ depositions.
The present invention has advantages below compared to existing technology：
（1）With stalk and the chloro- 2- Hydroxyproyl Trimethyls ammonium chlorides of 3-（CTA）For main production raw material, insoluble fiber in stalk
There is etherification reaction with the chloro- 2- Hydroxyproyl Trimethyls ammonium chlorides of 3- in element and lignin isoreactivity composition, generate cellulose anion
Etherate, a step obtain the biomass exchanger of surface band quaternary amine base.Then by oxide carried in the biological exchanger table
Face, finally gives the quaternary ammonium salt/oxide modifying biology hybrid material of simplified method preparation.This approach avoid and use N, N- diformazans
Multiple toxic chemical raw materials such as base formamide, epoxychloropropane, ethylenediamine, trimethylamine/triethylamine/urea and brought serious
Secondary pollution, cleans with process is simple, with low cost, the characteristics of raw material environmental friendliness, has while generation environment benefit
There is very high economic benefit.
（2）Contain abundant hydroxyl and carboxyl in the raw material stalk surface for utilizing of the present invention, it is easy to modified, so as to have
Adsorption capacity and the adsorptive selectivity of material are targetedly improved.The quaternary ammonium salt for preparing/oxide modifying biology hydridization material
Averagely per gram of material（In terms of Fe/La/Zr）Adsorbable 50 ~ 980mg of phosphorus, 50 ~ 890 mg of arsenic-adsorbing, adsorb 20 ~ 500mg of selenium.
（3）Compared with current material, such biological hybrid material treating capacity is greatly improved, and the electrostatic of existing quaternary amines is inhaled
The effect of drawing, the Coordination Adsorption effect for having nano inorganic oxide again, thus with higher adsorptive selectivity.Coexist compete from
Sub- NO3-、HCO3-、Cl-、SO4 2-Concentration be far above desired anion pollutant when, remain to realize micro amount of arsenic, selenium, phosphorus in water phase
Advanced treating with security control and renewable with recycle, and the material swellbility is less.
（4）Compared with current material, the biological hybrid material preparation technology is simple, little to raw material structure destruction, therefore
There is superior desorption and regeneration performance, the material after absorption can carry out desorption and regeneration by saline and alkaline mixed liquor, wherein salt is
NaCl or KCl, alkali are NaOH or KOH, and desorption temperature adopts 25 ~ 80 DEG C, after continuous 15 adsorption-desorption cycles, absorption effect
Fruit is still maintained at more than the 85% of initial adsorption amount, with good application potential.As shown in figure 4, loading oxygen with wheat stalk
As a example by changing zirconium absorption phosphate radical, when zirconium load capacity is 19%, after 15 adsorption-desorption cycles, the material is to phosphoric acid
The adsorption rate of root stills remain in more than the 85% of initial adsorption ability, regenerability is good, with actual application value.
（5）The present invention prepares quaternary ammonium salt/oxide modifying biology hybrid material, operating procedure letter using simplified method
Clean, it is achieved that waste straw recycling, while phosphorus, arsenic, the removal of selenium provide reliable technical support in water body.
Description of the drawings
Fig. 1 is biological for different amount of iron load（Wheat）Comparison diagram of the hybrid material to selenite radical treating capacity；
Fig. 2 carries lanthanum amount biology for different（Paddy rice）Comparison diagram of the hybrid material to phosphate radical treating capacity；
Fig. 3 carries zirconium amount biology for different（Corn）Comparison diagram of the hybrid material to arsenate treating capacity.
Fig. 4 is biological for carrying zirconium（Wheat）Circulation absorption-desorption curve of the hybrid material to phosphate radical.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
（1）Take 3g wheat stalks particle and 50mL mixed solvents（Methyl alcohol and the 5% NaOH aqueous solution are with volume ratio 1：1 mixing）Mixed
Close, then temperature programming is to 50 DEG C.Then by chloro- for 20mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）Speed with 5mL/min
Degree is uniformly dropped in mixed liquor, stirring reaction 1 hour at 50 DEG C.Product is washed to neutrality after filtration, 30 DEG C of vacuum drying 4
Hour, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 3g and add 10g FeCl3·6H2O and 35mL HCl（0.1mol/L）In mixed solution,
25 DEG C of stirring reactions 2 hours.Material filter screen is leached and is added in 50mL NaOH (5wt%) solution, 25 DEG C of stirring reactions 2
Hour.Product is washed to neutrality after end, is then washed with 5wt% NaCl solutions, deionized water, 25 DEG C of vacuum drying 6 are little
When, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 0.32 mmol/g, and iron load capacity is
2.1%.Experiment shows that biological hybrid material obtained above has obvious removal effect to selenite radical in water.Work as water body
Middle selenite radical content 3mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content be 10,20,20mg/L, raw water pH be 5 ± 0.2 when,
Selenite radical concentration can be down to 20 below g/L by above-mentioned biological hybrid material, reach national drinking water standard.
Embodiment 2
（1）Take 7g cassavas stalk particle and 50mL mixed solvents（Isopropanol and the 10% NaOH aqueous solution are with volume ratio 3：1 mixing）
Mixing, then temperature programming is to 60 DEG C.Then by chloro- for 35mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 10mL/min's
Speed is uniformly dropped in mixed liquor, stirring reaction 2 hours at 60 DEG C.Product is washed to neutrality after filtration, 40 DEG C of vacuum are done
Dry 6 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 5g and add 20g LaCl3·6H2O and 60mL HCl（0.3mol/L）In mixed solution,
40 DEG C of stirring reactions 3 hours.Material filter screen is leached and is added in 80mL NaOH (10wt%) solution, 40 DEG C of stirring reactions 4
Hour.Product is washed to neutrality after end, is then washed with 8wt% NaCl solutions, deionized water, 40 DEG C of vacuum drying 6 are little
When, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 0.45 mmol/g, and lanthanum load capacity is
4.5%.Experiment shows that biological hybrid material obtained above has obvious removal effect to phosphate radical in water.When in water body
Phosphate content 15mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content be 20,40,40mg/L, raw water pH be 6 ± 0.2 when, above-mentioned
Phosphate concentration can be down to 500 below g/L by biological hybrid material, reach national drinking water standard.
Embodiment 3
（1）Take 11g cotton stalks particle and 110mL mixed solvents（Ethanol and the 15% NaOH aqueous solution are with volume ratio 5：1 mixing）
Mixing, then temperature programming is to 70 DEG C.Then by chloro- for 60mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 20mL/min's
Speed is uniformly dropped in mixed liquor, stirring reaction 4 hours at 70 DEG C.Product is washed to neutrality after filtration, 50 DEG C of vacuum are done
Dry 10 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 10g and add 40g ZrOCl2·8H2O and 160mL HCl（0.5mol/L）Mixed solution
In, 50 DEG C of stirring reactions 6 hours.Material filter screen is leached and is added in 150mL NaOH (15wt%) solution, 50 DEG C of stirrings
Reaction 6 hours.Product is washed to neutrality after end, is then washed with 10wt% NaCl solutions, deionized water, 50 DEG C of vacuum are done
Dry 10 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 0.49 mmol/g, and zirconium load capacity is
4.3%.Experiment shows that biological hybrid material obtained above has obvious removal effect to arsenate in water.When in water body
8 mg/L of arsenic acid radical content, competing ions Cl‒、NO3 ‒、SO4 2‒Content be 25,50,50mg/L, raw water pH be 6 ± 0.2 when, above-mentioned
Arsenate root concentration can be down to 700 below g/L by biological hybrid material, and removal effect is good.
Embodiment 4
（1）Take 15g soybean stalks particle and 170mL mixed solvents（Isopropanol and the 20% NaOH aqueous solution are with volume ratio 5：1
Mixing）Mixing, then temperature programming is to 80 DEG C.Then by chloro- for 80mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 30mL/
The speed of min is uniformly dropped in mixed liquor, stirring reaction 6 hours at 80 DEG C.Product is washed to neutrality after filtration, 60 DEG C true
Empty dry 15 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 12 g and add 30g Fe (NO3)3·9H2O and 280mL HCl（0.7mol/L）Mixing is molten
In liquid, 60 DEG C of stirring reactions 8 hours.Material filter screen is leached and is added in 220mL NaOH (20wt%) solution, 60 DEG C are stirred
Mix reaction 8 hours.Product is washed to neutrality after end, is then washed with 20wt% NaCl solutions, deionized water, 60 DEG C of vacuum
Dry 16 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 0.8 mmol/g, and iron load capacity is
7.8%.Experiment shows that biological hybrid material obtained above has obvious removal effect to arsenate in water.When in water body
18 mg/L of arsenic acid radical content, competing ions Cl‒、NO3 ‒、SO4 2-Content be 25,50,50mg/L, raw water pH be 7 ± 0.2 when, on
State biological hybrid material and arsenate concentration can be down to 1mg/below L, removal effect is good.
Embodiment 5
（1）Take 22g rice straws particle and 280mL mixed solvents（Isopropanol and the 30% NaOH aqueous solution are with volume ratio 8：1 mixes
Close）Mixing, then temperature programming is to 100 DEG C.Then by chloro- for 100mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 40mL/
The speed of min is uniformly dropped in mixed liquor, stirring reaction 7 hours at 100 DEG C.Product is washed to neutrality after filtration, 80 DEG C
Vacuum drying 20 hours, obtains quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 18g and add 95g La (NO3)3·6H2O and 500mL HCl（0.8mol/L）Mixing is molten
In liquid, 80 DEG C of stirring reactions 10 hours.Material filter screen is leached and is added in 350mL NaOH (25wt%) solution, 75 DEG C are stirred
Mix reaction 10 hours.Product is washed to neutrality after end, is then washed with 25wt% NaCl solutions, deionized water, 75 DEG C true
Empty dry 20 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 1.0 mmol/g, and lanthanum load capacity is
8.4%.Experiment shows that biological hybrid material obtained above has obvious removal effect to phosphate radical in water.When in water body
30 mg/L of phosphate content, competing ions Cl‒、NO3 ‒、SO4 2-Content be 50,50,100mg/L, raw water pH be 6 ± 0.2 when, on
State biological hybrid material and phosphate concentration can be down to below 0.5mg/L, removal effect is good.
Embodiment 6
（1）Take 30g corn stalk pelletses and 600mL mixed solvents（Methyl alcohol and the 40% NaOH aqueous solution are with volume ratio 10:1 mixes
Close）Mixing, then temperature programming is to 120 DEG C.Then by chloro- for 150mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 60mL/
The speed of min is uniformly dropped in mixed liquor, stirring reaction 8 hours at 120 DEG C.Product is washed to neutrality after filtration, 80 DEG C
Vacuum drying 24 hours, obtains quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 20g and add 100g ZrOCl2·8H2O and 500mL HCl（1mol/L）Mixed solution
In, 80 DEG C of stirring reactions 12 hours.Material filter screen is leached and is added in 500 mL NaOH (30wt%) solution, 80 DEG C are stirred
Mix reaction 12 hours.Product is washed to neutrality after end, is then washed with 30wt% NaCl solutions, deionized water, 80 DEG C true
Empty dry 24 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 1.1 mmol/g, and zirconium load capacity is
16%.Experiment shows that biological hybrid material obtained above has obvious removal effect to phosphate radical in water.When phosphorus in water body
Acid group content 38mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content be 30,30,10mg/L, raw water pH be 7 ± 0.2 when, above-mentioned life
Phosphate concentration can be down to below 5mg/L by thing hybrid material, and removal effect is good.
Embodiment 7
（1）Take 8g wheat stalks particle and 150mL mixed solvents（Methyl alcohol and the 50%NaOH aqueous solution are with volume ratio 2.5：1 mixing）
Mixing, then temperature programming is to 80 DEG C.Then by chloro- for 55mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 7.5mL/min
Speed uniformly drop in mixed liquor, stirring reaction 3 hours at 80 DEG C.Product is washed to neutrality after filtration, 40 DEG C of vacuum
Dry 8 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 8g and add 60g FeCl3·6H2O and 200mL HCl（0.3mol/L）Mixed solution
In, 30 DEG C of stirring reactions 5 hours.Material filter screen is leached and is added in 200mL NaOH (5wt%) solution, 30 DEG C of stirrings are anti-
Answer 6 hours.Product is washed to neutrality after end, is then washed with 5wt% NaCl solutions, deionized water, 40 DEG C of vacuum drying 8
Hour, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 3.1mmol/g, and iron load capacity is
29.7%.The adsorption capacity of biomass composite is investigated below by Static Adsorption test：Prepare a series of 100mL phosphorus
Acid dihydride potassium solution, initial concentration（In terms of phosphorus）Respectively 5,10,20,30,40,60mg/L, background ions KNO in solution3Dense
Spend for 100mmol/L, pH is 7 ± 0.2, biological hybrid material dosage is 0.75g/L, concussion reaction 20 hours at 30 DEG C.Knot
Fruit shows that, as the adsorption capacity of the increase composite of initial concentration also gradually increases, maximum saturation adsorption capacity is reachable
38.2mg/g.
Embodiment 8
（1）Take 5g wheat stalks particle and 130mL mixed solvents（Methyl alcohol and the 20% NaOH aqueous solution are with volume ratio 3：1 mixing）
Mixing, then temperature programming is to 80 DEG C.Then by chloro- for 40mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 7.5mL/min
Speed uniformly drop in mixed liquor, stirring reaction 2 hours at 80 DEG C.Product is washed to neutrality after filtration, 40 DEG C of vacuum
Dry 8 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 5g and add 30g FeCl3·6H2O and 175mL HCl（0.3mol/L）Mixed solution
In, 30 DEG C of stirring reactions 5 hours.Material filter screen is leached and is added in 150mL NaOH (5wt%) solution, 30 DEG C of stirrings are anti-
Answer 6 hours.Product is washed to neutrality after end, is then washed with 5wt% NaCl solutions, deionized water, 40 DEG C of vacuum drying
10 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 1.6mmol/g, and iron load capacity is
18%.The adsorption capacity of biomass composite is investigated below by Static Adsorption test：Prepare a series of 100mL Asias selenium
Acid group, selenite radical initial concentration be 5,10,20,30,40,60mg/L, background ions KNO in solution3Concentration is 10mmol/
L, pH be 6.5 ± 0.2, biological hybrid material dosage be 0.5g/L, concussion reaction 24 hours at 40 DEG C.As a result show, with
The adsorption capacity of the increase composite of initial concentration also gradually increases, and maximum saturation adsorption capacity is up to 33.9 mg/g.
Embodiment 9
（1）Take 4g rice straws particle and 130mL mixed solvents（Methyl alcohol and the 20% NaOH aqueous solution are with volume ratio 3：1 mixing）
Mixing, then temperature programming is to 80 DEG C.Then by chloro- for 40mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 7.5mL/min
Speed uniformly drop in mixed liquor, stirring reaction 2 hours at 80 DEG C.Product is washed to neutrality after filtration, 40 DEG C of vacuum
Dry 8 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 5g and add 38g LaCl3·6H2O and 100mL HCl（0.6mol/L）Mixed solution
In, 30 DEG C of stirring reactions 12 hours.Material filter screen is leached and is added in 110mL NaOH (5wt%) solution, 30 DEG C of stirrings
Reaction 12 hours.Product is washed to neutrality after end, is then washed with 10wt% NaCl solutions, deionized water, 40 DEG C of vacuum
Dry 24 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biomass combined adsorbent obtained in the present embodiment, highly basic exchange capacity is 1.5mmol/g, lanthanum load capacity
For 15%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test：Prepare a series of 100mL phosphorous
Solution, phosphorus initial concentration are 10,20,40,60,80,100, background ions KNO in solution3100 mmol/L of concentration, pH be 7 ±
0.2, biological hybrid material dosage be 0.5g/L, concussion reaction 24 hours at 25 DEG C.As a result show, with the increasing of initial concentration
Plus the adsorption capacity of composite also gradually increases, maximum saturation adsorption capacity is up to 66.6mg/g.
Embodiment 10
（1）Take 4g corn stalk pelletses and 130mL mixed solvents（Methyl alcohol and the 20% NaOH aqueous solution are with volume ratio 3：1 mixing）
Mixing, then temperature programming is to 80 DEG C.Then by chloro- for 40mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 7.5mL/min
Speed uniformly drop in mixed liquor, stirring reaction 2 hours at 80 DEG C.Product is washed to neutrality after filtration, 40 DEG C of vacuum
Dry 8 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 5g and add 45g ZrOCl2·8H2O and 500mL HCl（1mol/L）In mixed solution,
80 DEG C of stirring reactions 12 hours.Material filter screen is leached and is added in 200mL NaOH (10 wt%) solution, 80 DEG C of stirrings are anti-
Answer 12 hours.Product is washed to neutrality after end, is then washed with 30wt% NaCl solutions, deionized water, 80 DEG C of vacuum are done
Dry 24 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biomass combined adsorbent obtained in the present embodiment, highly basic exchange capacity is 1.3mmol/g, zirconium load capacity
For 19%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test：A series of 100mL is prepared containing arsenic
Solution, arsenic initial concentration are 5,10,20,40,60,80,100, background ions KNO in solution3100 mmol/L of concentration, pH are 7
± 0.2, biological hybrid material dosage be 0.5g/L, concussion reaction 24 hours at 25 DEG C.As a result show, with initial concentration
The adsorption capacity for increasing composite also gradually increases, and maximum saturation adsorption capacity is up to 78.3mg/g.
Embodiment 11
（1）Take 5g soybean crops stalk particle and 100mL mixed solvents（Isopropanol and the 50%NaOH aqueous solution are with volume ratio 5：
1 mixing）Mixing, then temperature programming is to 60 DEG C.Then by chloro- for 80mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 5mL/
The speed of min is uniformly dropped in mixed liquor, stirring reaction 5 hours at 60 DEG C.Product is washed to neutrality after filtration, 50 DEG C true
Empty dry 12 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 5g and add 40g LaCl3·6H2O and 100mL HCl（0.6mol/L）Mixed solution
In, 30 DEG C of stirring reactions 12 hours.Material filter screen is leached and is added in 110mL NaOH (5wt%) solution, 30 DEG C of stirrings
Reaction 12 hours.Product is washed to neutrality after end, is then washed with 10wt% NaCl solutions, deionized water, 40 DEG C of vacuum
Dry 24 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biomass combined adsorbent obtained in the present embodiment, highly basic exchange capacity is 1.1mmol/g, lanthanum load capacity
For 22%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test：Prepare a series of 100mL phosphorous
Solution, phosphorus initial concentration are 10,20,40,60,80,100,150, background ions KNO in solution3100 mmol/L of concentration, pH are
7 ± 0.2, biological hybrid material dosage be 0.5g/L, concussion reaction 24 hours at 25 DEG C.As a result show, with initial concentration
Increase composite adsorption capacity also gradually increase, maximum saturation adsorption capacity is up to 50.6mg/g.
Embodiment 12
（1）Take 2.5g cotton agricultural crop straws particle and 80mL mixed solvents（Isopropanol and the 10% NaOH aqueous solution are with volume
Than 5：1 mixing）Mixing, then temperature programming is to 70 DEG C.Then by chloro- for 50mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With
The speed of 30mL/min is uniformly dropped in mixed liquor, stirring reaction 8 hours at 70 DEG C.Product is washed to neutrality after filtration,
50 DEG C are vacuum dried 16 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 2.5g and add 32g Fe (NO3)3·9H2O and 100mL HCl（0.25mol/L）Mixing
In solution, 25 DEG C of stirring reactions 8 hours.Material filter screen is leached and is added in 100mL NaOH (5wt%) solution, 25 DEG C are stirred
Mix reaction 12 hours.Product is washed to neutrality after end, is then washed with 5wt% NaCl solutions, deionized water, 25 DEG C of vacuum
Dry 12 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biological hybrid material obtained in the present embodiment, highly basic exchange capacity is 1.6 mmol/g, and iron load capacity is
23%.The adsorption capacity of biomass composite is investigated below by Static Adsorption test：A series of 100mL is prepared containing arsenic
Solution, the initial concentration of arsenate is 2.5mg/L, 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, background ions
NaNO3Concentration 50mmol/L, pH be 6 ± 0.2, biological hybrid material dosage be 0.5g/L, concussion reaction 24 hours at 25 DEG C.
As a result show, as the adsorption capacity of the increase composite of initial concentration also gradually increases, maximum saturation adsorption capacity is reachable
64.7mg/g.
Embodiment 13
（1）Take 10g cassavas stalk particle and 200mL mixed solvents（Isopropanol and the 50%NaOH aqueous solution are with volume ratio 8：1 mixes
Close）Mixing, then temperature programming is to 75 DEG C.Then by chloro- for 120mL 3- 2- Hydroxyproyl Trimethyl ammonium chlorides（CTA）With 1mL/
The speed of min is uniformly dropped in mixed liquor, stirring reaction 5 hours at 75 DEG C.Product is washed to neutrality after filtration, 50 DEG C true
Empty dry 12 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
（2）Weigh the above-mentioned biological exchangers of 5g and add 50g ZrOCl2·8H2O and 200mL HCl（0.6mol/L）Mixed solution
In, 40 DEG C of stirring reactions 16 hours.Material filter screen is leached and is added in 150mL NaOH (5wt%) solution, 40 DEG C of stirrings
Reaction 8 hours.Product is washed to neutrality after end, is then washed with 7.5wt% NaCl solutions, deionized water, 40 DEG C of vacuum
Dry 24 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material.
Using biomass combined adsorbent obtained in the present embodiment, highly basic exchange capacity is 1.2mmol/g, zirconium load capacity
For 26%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test：Prepare a series of 100mL phosphorous
Solution, phosphorus initial concentration are 5,10,20,40,60,80, background ions KNO in solution35 mmol/L of concentration, pH be 4.5 ±
0.2, biological hybrid material dosage be 0.5g/L, concussion reaction 24 hours at 25 DEG C.As a result show, with the increasing of initial concentration
Plus the adsorption capacity of composite also gradually increases, maximum saturation adsorption capacity is up to 32.2mg/g.
Embodiment 14
From embodiment 1,4,7,12 it can be seen that carrying iron biology hybrid material to selenite radical, arsenate, phosphate radical with stronger
Disposal ability.By taking selenite radical as an example, process energy of the material to selenite radical can be further investigated by post adsorption experiment
Power.Specific experiment step is as follows：Prepare simulation waste water containing selenite radical：Initial selenium concentration is 1mg/L, NO3 ‒、Cl‒、SO4 2‒Content
Respectively 20,20,10mg/L, raw water pH be 6 ± 0.2, biomass composite consumption be 10 mL, flow velocity is 15-30min/
BV, in water outlet selenium concentration less than on the premise of 0.1 mg/L, different quaternary ammonium group contents obtained in technique produced according to the present invention and
The biomass combined adsorbent of different iron contents is 95-2200BV to the treating capacity of selenium.
As shown in figure 1, with the increase of iron content in biological hybrid material, its adsorbance to selenite radical gradually increases
Plus, when iron load capacity reaches 18%, selenate radical adsorbance reaches maximum.When iron load capacity continues to increase, adsorbance is in decline
Trend, this are to cause adsorption site to block as iron load capacity is too high, so as to cause adsorbance to reduce.Consider adsorption effect with
Preparation cost, it is 18% to carry the optimal iron load capacity of iron biology hybrid material.
Embodiment 15
From embodiment 2,5,9,11 it can be seen that carrying lanthanum biology hybrid material has stronger disposal ability to phosphate radical, can pass through
Post adsorption experiment is further investigating disposal ability of the material to phosphate radical.Specific experiment step is as follows：Prepare simulation phosphorous useless
Water：Phosphorus concentration is 5mg/L, NO3 ‒、Cl‒、SO4 2‒Content respectively 50,50,25mg/L, raw water pH is 5 ± 0.2, hybrid material
Consumption is 5mL, and flow velocity is 15-30min/BV, on the premise of water outlet phosphorus concentration is less than 0.5mg/L, work produced according to the present invention
The lanthanum hybrid material that carries of different quaternary ammonium group contents obtained in skill and different lanthanum contents is 150-5800 BV to the treating capacity of phosphorus.
As shown in Fig. 2 with the increase of lanthanum content in biological hybrid material, its adsorbance to phosphate radical gradually increases,
When lanthanum load capacity reaches 15%, Phosphateadsorption amount reaches maximum.When lanthanum load capacity continues to increase, adsorbance becomes in decline
Gesture, this are to cause adsorption site to block as lanthanum load capacity is too high, so as to cause adsorbance to reduce.Consider adsorption effect and system
Standby cost, the load capacity for carrying the optimal lanthanum of lanthanum biology hybrid material is 15%.
Embodiment 16
From embodiment 3,6,10,13 it can be seen that carrying zirconium biology hybrid material has stronger process energy to phosphate radical, arsenate
Power.By taking arsenate as an example, carry zirconium biology hybrid material and place of the material to arsenate can be further investigated by post adsorption experiment
Reason ability.Specific experiment step is as follows：Prepare simulation waste water containing arsenate：Arsenic concentration is 3mg/L, NO3 ‒、Cl‒、SO4 2‒Content point
Not Wei 50,50,100mg/L, raw water pH be 4.5 ± 0.2, biomass composite consumption be 7.5mL, flow velocity is 15-30min/
BV, in water outlet phosphorus concentration less than on the premise of 0.5mg/L, different quaternary ammonium group contents obtained in technique produced according to the present invention and
The biomass combined adsorbent of different zirconium contents is 80-3200 BV to the treating capacity of arsenate.
As shown in figure 3, with the increase of zirconium content in biological hybrid material, its adsorbance to arsenate gradually increases,
When zirconium load capacity reaches 19%, Arsenate adsorption amount reaches maximum.When zirconium load capacity continues to increase, adsorbance becomes in decline
Gesture, this are to cause adsorption site to block as zirconium load capacity is too high, so as to cause adsorbance to reduce.Consider adsorption effect and system
Standby cost, the load capacity for carrying the optimal zirconium of zirconium biology hybrid material is 19%.
Claims (8)
1. the preparation method of a kind of quaternary ammonium salt/oxide modifying biology hybrid material, it is characterised in that：The biological hybrid material
With stalk as raw material, adopt the chloro- 2- Hydroxyproyl Trimethyls ammonium chlorides of 3- to be modified for etherifying agent, prepare cellulose cloudy from
Sub- etherate；Then in its area load metal oxide, the quaternary ammonium salt/oxide modifying biology hybrid material is obtained final product；Institute
Metal oxide is stated for iron oxide, lanthana or zirconium oxide.
2. preparation method according to claim 1, it is characterised in that：The metal oxide is nano-oxide particles；
When the metal oxide is iron oxide, on the biological hybrid material, the load capacity of iron is 2-31 wt %；When the metal
When oxide is lanthana, on the biological hybrid material, the load capacity of lanthanum is 1-24 wt %；When the metal oxide is oxygen
When changing zirconium, on the biological hybrid material, the load capacity of zirconium is 1-27 wt %.
3. preparation method according to claim 2, it is characterised in that：The biological hybrid material is with wheat stalk as original
Material, the load capacity of iron is 18%.
4. preparation method according to claim 2, it is characterised in that：The biological hybrid material is with rice straw as original
Material, the load capacity of lanthanum is 15%.
5. preparation method according to claim 2, it is characterised in that：The biological hybrid material is with maize straw as original
Material, the load capacity of zirconium is 19%.
6. preparation method according to claim 2, it is characterised in that：The preparation method of the biological hybrid material is as follows：
（1）The preparation of cellulose anion etherate：Take 2-30g agricultural crop straws particle to mix with 20-600mL mixed solvents,
It is warming up to 50-120 DEG C；Then the chloro- 2- hydroxypropyl trimethylammoniums of 10-150mL 3- are uniformly added dropwise with the speed of 2-60mL/min thereto
Base ammonium chloride, stirring reaction 0.5-8 hour at 50-120 DEG C；After reaction terminates, filter, product is washed to neutrality, 25-80
DEG C vacuum drying 2-24 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；The mixed solvent is using organic molten
Agent is with the NaOH aqueous solution with volume ratio 0.1：1-10：1 is mixed with, and organic solvent adopts methyl alcohol, isopropanol or ethanol, NaOH
The concentration of the aqueous solution is 1-50%；
（2）Metal oxide supported：The chlorate or nitrate or zirconium oxychloride for taking 2-100g metals adds 10-500mL HCl
The aqueous solution prepares mixed solution, adds the above-mentioned biological exchangers of 1-20g, 25-80 DEG C of stirring reaction 1-12 hour；Reaction terminates
Afterwards, filter screen is leached, and filter residue material is added in the 10-500mL NaOH aqueous solution, 25-80 DEG C of stirring reaction 1-12 hour；Instead
After should terminating, product is washed to neutrality, is then washed with the NaCl solution of 5-30wt%, deionized water successively, 25-80 DEG C true
Sky dries 2-24 hours, that is, obtain quaternary ammonium salt/oxide modifying biology hybrid material；The metal is from iron or lanthanum；The HCl
The concentration of the aqueous solution is 0.1-1mol/L；The concentration of the NaOH aqueous solution is 2-30wt%.
7. preparation method according to claim 6, it is characterised in that：The agricultural crop straw particle from wheat stalk,
Mixture more than rice straw, cotton stalk, maize straw, soybean stalk, cassava stalk or both；The agricultural crop straw
The particle size of particle is 0.2-1.5mm.
8. preparation method according to claim 6, it is characterised in that：The step（1）It is organic that middle mixed solvent is adopted
Solvent is isopropanol.
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