CN106492765B - 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
- Publication number
- CN106492765B CN106492765B CN201611004077.1A CN201611004077A CN106492765B CN 106492765 B CN106492765 B CN 106492765B CN 201611004077 A CN201611004077 A CN 201611004077A CN 106492765 B CN106492765 B CN 106492765B
- Authority
- CN
- China
- Prior art keywords
- hybrid material
- biology
- oxide
- hours
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J2220/4812—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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of quaternary ammonium salt/oxide modifying biology hybrid material preparation method, present invention biology hybrid material uses the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride of 3- to be modified for etherifying agent, cellulose anion etherate is prepared using stalk as raw material；Then in its area load metal oxide to get quaternary ammonium salt/oxide modifying biology hybrid material；Wherein metal oxide is iron oxide, lanthana or zirconium oxide.The present invention is nontoxic using materials safety, and synthesis technology is simple, environmentally protective.
Description
Technical field
The present invention relates to a kind of preparation methods of biological hybrid material modified with quaternary ammonium salt and nano-oxide, can apply
In a variety of processing containing the anionics pollutant waste water such as arsenic, selenium, phosphorus, belongs to wastewater treatment and agricultural resources and utilize field.
Background technique
Arsenic and selenium are typical poisonous and harmful elements, have extremely strong toxicity to biology including people, phosphorus then draws
Play one of the key reason of water eutrophication, and a kind of non-renewable precious mineral resources.Therefore, no matter go back at home
It is that in the world, the content of arsenic in water body, selenium and phosphorus has stringent restriction.In addition, China is large agricultural country, generate every year several hundred million
Ton stalk carries out improper disposition (such as burning) to it and has resulted in serious atmosphere pollution.Therefore, the resource of agricultural waste material
Change to utilize and have become one of environmental problem of greatest concern, while realizing the deep treatment and reality of arsenic in water body, selenium and phosphorus pollution
The resource utilization of existing biomass straw is of great significance.
Cellulose, hemicellulose and lignin rich in stalk containing a large amount of there is reaction to live in the structure
Property hydroxyl group, be conducive to carry out surface modified.Existing research at present uses discarded agricultural crop straw as raw material, by band
The quaternary ammonium group of positive charge is modified in stalk channel surfaces, and metal oxide (lanthana) is supported on modified straw again on this basis
On stalk, being prepared has highly selective quaternary ammonium salt/oxide modifying biology hybrid material (CN to anionic pollutant
105214629 A).But during modification aminated to stalk, N, N- dimethylformamide, epoxy chloropropionate are used
A variety of toxic chemical raw materials such as alkane, ethylenediamine, trimethylamine/triethylamine/urea, synthesis technology is complicated and generates harmful by-products,
Secondary pollution is serious.
Summary of the invention
The purpose of the present invention is to solve defect existing in the prior art, provide that a kind of materials safety is nontoxic, synthesis
Simple process and environmentally protective quaternary ammonium salt/oxide modifying biology hybrid material preparation method.
In order to achieve the above object, the present invention provides a kind of preparations of quaternary ammonium salt/oxide modifying biology hybrid material
Method, present invention biology hybrid material use the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride of 3- for etherifying agent progress using stalk as raw material
It is modified, cellulose anion etherate is prepared；Then in its area load metal oxide to get quaternary ammonium salt/oxide
Modification biological hybrid material；Wherein metal oxide is iron oxide, lanthana or zirconium oxide.
It is metal oxide supported to use in situ deposition method.
Wherein, metal oxide is nano-oxide particles；It is by the method for in-situ deposition that its is immobilized in biology exchange
Quaternary ammonium salt/oxide modifying biology hybrid material is made in agent surface, and load capacity weight percent in terms of iron is 2-31%, in terms of lanthanum
Weight percent is 1-24%, and weight percent is 1-27% in terms of zirconium.
Quaternary ammonium salt of the present invention/oxide modifying biology hybrid material it is specific the preparation method is as follows:
(1) mono- step of CTA is modified: take 2-30g agricultural crop straw particle and 20-600mL methanol/isopropanol/ethyl alcohol and
The mixed solvent (volume ratio 0.1:1-10:1) of NaOH aqueous solution (volumetric concentration 1-50%) mixes, and then temperature programming is extremely
50-120℃.Then the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 10-150mL 3- is uniform with the speed of 2-60mL/min
It is added dropwise in mixed liquor, is stirred to react at 50-120 DEG C 0.5-8 hours.Product is washed to neutrality, 25-80 DEG C of vacuum after filtering
It is 2-24 hours dry, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) metal oxide supported: to weigh the above-mentioned biological exchanger of 1-20g and 2-100g iron/lanthanum chlorate or nitre is added
With 10-500mL HCl(0.1-1mol/L) mixed solution, 25-80 DEG C is stirred to react 1-12 hours for hydrochlorate or zirconium oxychloride.
Material is filtered out with strainer and is added in 10-500mL NaOH (2-30wt%) solution, 25-80 DEG C is stirred to react 1-12 hours.
After product is washed to neutrality, then washed with 5-30wt% NaCl solution, deionized water, 25-80 DEG C of vacuum drying 2-
24 hours to get arrive quaternary ammonium salt/oxide modifying biology hybrid material.
Wherein, agricultural crop straw includes wheat stalk, rice straw, cotton stalk, corn stover, soybean stalk, cassava
Or mixtures thereof stalk, preferably wheat stalk, rice straw, corn stover, cotton stalk.Average grain diameter is between 0.2-
Between 1.5mm.
Preferably, organic solvent used is isopropanol in mono- step modifying process of CTA.
When iron oxide loads, the load capacity of iron preferably 18% is added with 5g biology exchanger (being prepared using wheat stalk)
30g FeCl3·6H2The preparation of O in-situ deposition.
When lanthana loads, the load capacity of lanthanum preferably 15% is added with 4g biology exchanger (being prepared using rice straw)
38 g La(NO3)3·6H2The preparation of O in-situ deposition.
When zirconium oxide loads, the load capacity of zirconium preferably 19% is added with 6g biology exchanger (being prepared using corn stover)
45g ZrOCl2·8H2The preparation of O in-situ deposition.
The present invention has the advantage that compared with prior art
(1) insoluble in stalk with stalk and the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 3- for main production raw material
Etherification reaction occurs for cellulose and the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride of lignin isoreactivity ingredient and 3-, generates cellulose yin
Ion etherate, a step obtain biomass exchanger of the surface with quaternary amine base.Then it is exchanged oxide carried in the biology
Agent surface finally obtains quaternary ammonium salt/oxide modifying biology hybrid material of simplified method preparation.This approach avoid use N, N-
A variety of toxic chemical raw materials such as dimethylformamide, epoxychloropropane, ethylenediamine, trimethylamine/triethylamine/urea and brought
Serious secondary pollution has simple process cleaning, low in cost, the environmental-friendly feature of raw material, in the same of generation environment benefit
When have very high economic benefit.
(2) the raw material stalk surface hydroxyl rich in utilized and carboxyl of the invention, it is easily modified, so as to have
Targetedly improve the adsorption capacity and adsorptive selectivity of material.The quaternary ammonium salt being prepared/oxide modifying biology hydridization material
Expect average every gram of adsorbable 50 ~ 980mg of phosphorus (in terms of Fe/La/Zr), 50 ~ 890 mg of arsenic-adsorbing, adsorbs 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, and there is the Coordination Adsorption of nano inorganic oxide to act on, thus adsorptive selectivity with higher.Coexist competition from
Sub- NO3-、HCO3-、Cl-、SO4 2-Concentration be much higher than desired anion pollutant when, be still able to achieve micro amount of arsenic in water phase, selenium, phosphorus
Advanced treating and security control and it is renewable with recycle, and the material swellbility is smaller.
(4) compared with current material, biology hybrid material preparation process is simple, small to raw material structure destruction, therefore
With superior desorption and regeneration performance, the material after absorption can carry out desorption and regeneration by saline and alkaline mixed liquor, and wherein salt is
NaCl or KCl, alkali are NaOH or KOH, and desorption temperature uses 25 ~ 80 DEG C, after continuous 15 adsorption-desorption cycles, absorption effect
Fruit is still maintained at 85% or more of initial adsorption amount, has good application potential.As shown in figure 4, loading oxygen with wheat stalk
For 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 85% or more of initial adsorption ability, regenerability is good, has practical application value.
(5) quaternary ammonium salt/oxide modifying biology hybrid material, operating procedure letter is prepared using simplified method in the present invention
It is clean, waste straw resource utilization is realized, while the removal of phosphorus, arsenic, selenium provides reliable technical support in water body.
Detailed description of the invention
Fig. 1 is comparison diagram of biological (wheat) hybrid material of different amount of iron load to selenite radical treating capacity；
Fig. 2 is comparison diagram of different biological (rice) hybrid materials of load lanthanum amount to phosphate radical treating capacity；
Fig. 3 is comparison diagram of different biological (corn) hybrid materials of load zirconium amount to arsenate treating capacity.
Fig. 4 is to carry biological (wheat) hybrid material of zirconium to circulation absorption-desorption curve of phosphate radical.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1
(1) take 3g wheat stalk particle and 50mL mixed solvent (methanol and 5% NaOH aqueous solution are mixed with volume ratio 1:1)
Mixing, then temperature programming is to 50 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 20mL 3- with 5mL/min's
Speed is dropped evenly into mixed liquor, is stirred to react at 50 DEG C 1 hour.Product is washed to neutrality after filtering, 30 DEG C of vacuum are dry
Dry 4 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 3g and 10g FeCl is added3·6H2O and 35mL HCl(0.1mol/L) mixed solution
In, 25 DEG C are stirred to react 2 hours.Material is filtered out with strainer and is added in 50mL NaOH (5wt%) solution, 25 DEG C of stirrings are anti-
It answers 2 hours.After product is washed to neutrality, then washed with 5wt% NaCl solution, deionized water, 25 DEG C of vacuum drying 6
Hour to get arrive quaternary ammonium salt/oxide modifying biology hybrid material.
Using biology hybrid material made from 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 apparent removal effect to selenite radical in water.Work as water body
Middle selenite radical content 3mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content is 10,20,20mg/L, when raw water pH is 5 ± 0.2,
Selenite radical concentration can be down to 20 μ g/L hereinafter, reaching national drinking water standard by above-mentioned biology hybrid material.
Embodiment 2
(1) taking 7g cassava stalk particle with 50mL mixed solvent, (isopropanol and 10% NaOH aqueous solution are with volume ratio 3:1
Mixing) mixing, then temperature programming is to 60 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 35mL 3- with 10mL/
The speed of min is dropped evenly into mixed liquor, is stirred to react at 60 DEG C 2 hours.Product is washed to neutrality after filtering, 40 DEG C true
Sky is 6 hours dry, obtains quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 5g and 20g LaCl is added3·6H2O and 60mL HCl(0.3mol/L) mixed solution
In, 40 DEG C are stirred to react 3 hours.Material is filtered out with strainer and is added in 80mL NaOH (10wt%) solution, 40 DEG C of stirrings are anti-
It answers 4 hours.After product is washed to neutrality, then washed with 8wt% NaCl solution, deionized water, 40 DEG C of vacuum drying 6
Hour to get arrive quaternary ammonium salt/oxide modifying biology hybrid material.
Using biology hybrid material made from 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 apparent 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, it is above-mentioned
Phosphate concentration can be down to 500 μ g/L hereinafter, reaching national drinking water standard by biological hybrid material.
Embodiment 3
(1) taking 11g cotton stalk particle and 110mL mixed solvent, (ethyl alcohol and 15% NaOH aqueous solution are mixed with volume ratio 5:1
Close) mixing, then temperature programming is to 70 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 60mL 3- with 20mL/
The speed of min is dropped evenly into mixed liquor, is stirred to react at 70 DEG C 4 hours.Product is washed to neutrality after filtering, 50 DEG C true
Sky is 10 hours dry, obtains quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 10g and 40g ZrOCl is added2·8H2O is mixed with 160mL HCl(0.5mol/L)
In solution, 50 DEG C are stirred to react 6 hours.Material is filtered out with strainer and is added in 150mL NaOH (15wt%) solution, 50 DEG C
It is stirred to react 6 hours.After product is washed to neutrality, then washed with 10wt% NaCl solution, deionized water, 50 DEG C are true
Sky dries 10 hours to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biology hybrid material made from 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 apparent removal effect to arsenate in water.When in water body
Arsenic acid radical content 8 mg/L, competing ions Cl‒、NO3 ‒、SO4 2‒Content be 25,50,50mg/L, raw water pH be 6 ± 0.2 when, it is above-mentioned
Arsenate root concentration can be down to 700 μ g/L hereinafter, removal effect is good by biological hybrid material.
Embodiment 4
(1) taking 15g soybean stalk particle with 170mL mixed solvent, (isopropanol and 20% NaOH aqueous solution are with volume ratio
5:1 mixing) mixing, then temperature programming is to 80 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 80mL 3- with
The speed of 30mL/min is dropped evenly into mixed liquor, is stirred to react at 80 DEG C 6 hours.Product is washed to neutrality after filtering,
60 DEG C are dried in vacuo 15 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 12 g and 30g Fe (NO is added3)3·9H2O and 280mL HCl(0.7mol/L) it is mixed
It closes in solution, 60 DEG C are stirred to react 8 hours.Material is filtered out with strainer and is added in 220mL NaOH (20wt%) solution, 60
It DEG C is stirred to react 8 hours.After product is washed to neutrality, then washed with 20wt% NaCl solution, deionized water, 60 DEG C
16 hours are dried in vacuo to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biology hybrid material made from 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 apparent removal effect to arsenate in water.When in water body
Arsenic acid radical content 18 mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content is 25,50,50mg/L, when raw water pH is 7 ± 0.2, on
1mg/L can be down to for arsenate concentration hereinafter, removal effect is good by stating biological hybrid material.
Embodiment 5
(1) taking 22g rice straw particle with 280mL mixed solvent, (isopropanol and 30% NaOH aqueous solution are with volume ratio
8:1 mixing) mixing, then temperature programming is to 100 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 100mL 3- with
The speed of 40mL/min is dropped evenly into mixed liquor, is stirred to react at 100 DEG C 7 hours.Product is washed to neutrality after filtering,
80 DEG C are dried in vacuo 20 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 18g and 95g La (NO is added3)3·6H2O and 500mL HCl(0.8mol/L) it is mixed
It closes in solution, 80 DEG C are stirred to react 10 hours.Material is filtered out with strainer and is added in 350mL NaOH (25wt%) solution, 75
It DEG C is stirred to react 10 hours.After product is washed to neutrality, then washed with 25wt% NaCl solution, deionized water, 75
DEG C vacuum drying 20 hours to get arrive quaternary ammonium salt/oxide modifying biology hybrid material.
Using biology hybrid material made from 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 apparent removal effect to phosphate radical in water.When in water body
Phosphate content 30 mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content is 50,50,100mg/L, when raw water pH is 6 ± 0.2, on
0.5mg/L can be down to for phosphate concentration hereinafter, removal effect is good by stating biological hybrid material.
Embodiment 6
(1) take 30g corn stalk pellets and 600mL mixed solvent (methanol and 40% NaOH aqueous solution are with volume ratio 10:
1 mixing) mixing, then temperature programming is to 120 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 150mL 3- with
The speed of 60mL/min is dropped evenly into mixed liquor, is stirred to react at 120 DEG C 8 hours.Product is washed to neutrality after filtering,
80 DEG C are dried in vacuo 24 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 20g and 100g ZrOCl is added2·8H2O mixes molten with 500mL HCl(1mol/L)
In liquid, 80 DEG C are stirred to react 12 hours.Material is filtered out with strainer and is added in 500 mL NaOH (30wt%) solution, 80 DEG C
It is stirred to react 12 hours.After product is washed to neutrality, then washed with 30wt% NaCl solution, deionized water, 80 DEG C
24 hours are dried in vacuo to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biology hybrid material made from 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 apparent removal effect to phosphate radical in water.When phosphorus in water body
Acid group content 38mg/L, competing ions Cl‒、NO3 ‒、SO4 2-Content is 30,30,10mg/L, when raw water pH is 7 ± 0.2, above-mentioned life
Phosphate concentration can be down to 5mg/L hereinafter, removal effect is good by object hybrid material.
Embodiment 7
(1) taking 8g wheat stalk particle with 150mL mixed solvent, (methanol and 50%NaOH aqueous solution are with volume ratio 2.5:1
Mixing) mixing, then temperature programming is to 80 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 55mL 3- with
The speed of 7.5mL/min is dropped evenly into mixed liquor, is stirred to react at 80 DEG C 3 hours.Product is washed to neutrality after filtering,
40 DEG C are dried in vacuo 8 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 8g and 60g FeCl is added3·6H2O mixes molten with 200mL HCl(0.3mol/L)
In liquid, 30 DEG C are stirred to react 5 hours.Material is filtered out with strainer and is added in 200mL NaOH (5wt%) solution, 30 DEG C of stirrings
Reaction 6 hours.After product is washed to neutrality, then washed with 5wt% NaCl solution, deionized water, 40 DEG C of vacuum are dry
Dry 8 hours to get arrive quaternary ammonium salt/oxide modifying biology hybrid material.
Using biology hybrid material made from 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: preparing a series of 100mL phosphorus
Acid dihydride potassium solution, initial concentration (in terms of phosphorus) are respectively 5,10,20,30,40,60mg/L, background ions KNO in solution3It is dense
Degree is 100mmol/L, and pH is 7 ± 0.2, and 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 material of initial concentration also gradually increases, maximum saturation adsorption capacity is reachable
38.2mg/g。
Embodiment 8
(1) taking 5g wheat stalk particle and 130mL mixed solvent, (methanol and 20% NaOH aqueous solution are mixed with volume ratio 3:1
Close) mixing, then temperature programming is to 80 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 40mL 3- with 7.5mL/
The speed of min is dropped evenly into mixed liquor, is stirred to react at 80 DEG C 2 hours.Product is washed to neutrality after filtering, 40 DEG C true
Sky is 8 hours dry, obtains quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 5g and 30g FeCl is added3·6H2O mixes molten with 175mL HCl(0.3mol/L)
In liquid, 30 DEG C are stirred to react 5 hours.Material is filtered out with strainer and is added in 150mL NaOH (5wt%) solution, 30 DEG C of stirrings
Reaction 6 hours.After product is washed to neutrality, then washed with 5wt% NaCl solution, deionized water, 40 DEG C of vacuum are dry
Dry 10 hours to get arrive quaternary ammonium salt/oxide modifying biology hybrid material.
Using biology hybrid material made from 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: preparing a series of Asia 100mL selenium
Acid group, selenite radical initial concentration are 5,10,20,30,40,60mg/L, background ions KNO in solution3Concentration is 10mmol/
L, pH are 6.5 ± 0.2, and biological hybrid material dosage is 0.5g/L, concussion reaction 24 hours at 40 DEG C.The results show that with
The adsorption capacity of the increase composite material of initial concentration also gradually increases, and maximum saturation adsorption capacity is up to 33.9 mg/g.
Embodiment 9
(1) taking 4g rice straw particle and 130mL mixed solvent, (methanol and 20% NaOH aqueous solution are mixed with volume ratio 3:1
Close) mixing, then temperature programming is to 80 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 40mL 3- with 7.5mL/
The speed of min is dropped evenly into mixed liquor, is stirred to react at 80 DEG C 2 hours.Product is washed to neutrality after filtering, 40 DEG C true
Sky is 8 hours dry, obtains quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 5g and 38g LaCl is added3·6H2O mixes molten with 100mL HCl(0.6mol/L)
In liquid, 30 DEG C are stirred to react 12 hours.Material is filtered out with strainer and is added in 110mL NaOH (5wt%) solution, 30 DEG C are stirred
Mix reaction 12 hours.After product is washed to neutrality, then washed with 10wt% NaCl solution, deionized water, 40 DEG C are true
Sky dries 24 hours to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biomass combined adsorbent made from the present embodiment, highly basic exchange capacity is 1.5mmol/g, lanthanum load capacity
It is 15%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test: it is phosphorous to prepare a series of 100mL
Solution, phosphorus initial concentration are 10,20,40,60,80,100, background ions KNO in solution3Concentration 100 mmol/L, pH be 7 ±
0.2, biological hybrid material dosage is 0.5g/L, concussion reaction 24 hours at 25 DEG C.The results show that with the increasing of initial concentration
The adsorption capacity of composite material is added also to gradually increase, maximum saturation adsorption capacity is up to 66.6mg/g.
Embodiment 10
(1) taking 4g corn stalk pellets and 130mL mixed solvent, (methanol and 20% NaOH aqueous solution are mixed with volume ratio 3:1
Close) mixing, then temperature programming is to 80 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 40mL 3- with 7.5mL/
The speed of min is dropped evenly into mixed liquor, is stirred to react at 80 DEG C 2 hours.Product is washed to neutrality after filtering, 40 DEG C true
Sky is 8 hours dry, obtains quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 5g and 45g ZrOCl is added2·8H2O and 500mL HCl(1mol/L) mixed solution
In, 80 DEG C are stirred to react 12 hours.Material is filtered out with strainer and is added in 200mL NaOH (10 wt%) solution, 80 DEG C are stirred
Mix reaction 12 hours.After product is washed to neutrality, then washed with 30wt% NaCl solution, deionized water, 80 DEG C are true
Sky dries 24 hours to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biomass combined adsorbent made from the present embodiment, highly basic exchange capacity is 1.3mmol/g, zirconium load capacity
It is 19%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test: preparing a series of 100mL containing arsenic
Solution, arsenic initial concentration are 5,10,20,40,60,80,100, background ions KNO in solution3Concentration 100 mmol/L, pH 7
± 0.2, biological hybrid material dosage is 0.5g/L, concussion reaction 24 hours at 25 DEG C.The results show that with initial concentration
The adsorption capacity for increasing composite material also gradually increases, and maximum saturation adsorption capacity is up to 78.3mg/g.
Embodiment 11
(1) taking 5g soybean crop stalk particle with 100mL mixed solvent, (isopropanol and 50%NaOH aqueous solution are with volume
Mixed than 5:1) mixing, then temperature programming is to 60 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 80mL 3- with
The speed of 5mL/min is dropped evenly into mixed liquor, is stirred to react at 60 DEG C 5 hours.Product is washed to neutrality after filtering, 50
DEG C vacuum drying 12 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 5g and 40g LaCl is added3·6H2O mixes molten with 100mL HCl(0.6mol/L)
In liquid, 30 DEG C are stirred to react 12 hours.Material is filtered out with strainer and is added in 110mL NaOH (5wt%) solution, 30 DEG C are stirred
Mix reaction 12 hours.After product is washed to neutrality, then washed with 10wt% NaCl solution, deionized water, 40 DEG C are true
Sky dries 24 hours to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biomass combined adsorbent made from the present embodiment, highly basic exchange capacity is 1.1mmol/g, lanthanum load capacity
It is 22%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test: it is phosphorous to prepare a series of 100mL
Solution, phosphorus initial concentration are 10,20,40,60,80,100,150, background ions KNO in solution3Concentration 100 mmol/L, pH are
7 ± 0.2, biological hybrid material dosage is 0.5g/L, concussion reaction 24 hours at 25 DEG C.The results show that with initial concentration
The adsorption capacity of increase composite material also gradually increase, maximum saturation adsorption capacity is up to 50.6mg/g.
Embodiment 12
(1) take 2.5g cotton agricultural crop straw particle and 80mL mixed solvent (isopropanol and 10% NaOH aqueous solution with
Volume ratio 5:1 mixing) mixing, then temperature programming is to 70 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride of 50mL 3-
(CTA) it is dropped evenly with the speed of 30mL/min into mixed liquor, is stirred to react at 70 DEG C 8 hours.Product is washed after filtering
To neutrality, 50 DEG C are dried in vacuo 16 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 2.5g and 32g Fe (NO is added3)3·9H2O and 100mL HCl(0.25mol/L)
In mixed solution, 25 DEG C are stirred to react 8 hours.Material is filtered out with strainer and is added in 100mL NaOH (5wt%) solution, 25
It DEG C is stirred to react 12 hours.After product is washed to neutrality, then washed with 5wt% NaCl solution, deionized water, 25 DEG C
12 hours are dried in vacuo to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biology hybrid material made from 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: preparing a series of 100mL containing arsenic
Solution, the initial concentration of arsenate are 2.5mg/L, 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, background ions
NaNO3Concentration 50mmol/L, pH are 6 ± 0.2, and biological hybrid material dosage is 0.5g/L, concussion reaction 24 hours at 25 DEG C.
The results show that maximum saturation adsorption capacity is reachable as the adsorption capacity of the increase composite material of initial concentration also gradually increases
64.7mg/g。
Embodiment 13
(1) taking 10g cassava stalk particle with 200mL mixed solvent, (isopropanol and 50%NaOH aqueous solution are with volume ratio 8:1
Mixing) mixing, then temperature programming is to 75 DEG C.Then by the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride (CTA) of 120mL 3- with 1mL/
The speed of min is dropped evenly into mixed liquor, is stirred to react at 75 DEG C 5 hours.Product is washed to neutrality after filtering, 50 DEG C true
Sky is 12 hours dry, obtains quaternary ammonium salt-modified anionic biology exchanger；
(2) it weighs the above-mentioned biological exchanger of 5g and 50g ZrOCl is added2·8H2O mixes molten with 200mL HCl(0.6mol/L)
In liquid, 40 DEG C are stirred to react 16 hours.Material is filtered out with strainer and is added in 150mL NaOH (5wt%) solution, 40 DEG C are stirred
Mix reaction 8 hours.After product is washed to neutrality, then washed with 7.5wt% NaCl solution, deionized water, 40 DEG C are true
Sky dries 24 hours to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived.
Using biomass combined adsorbent made from the present embodiment, highly basic exchange capacity is 1.2mmol/g, zirconium load capacity
It is 26%.The adsorption capacity of biological hybrid material is investigated below by Static Adsorption test: it is phosphorous to prepare a series of 100mL
Solution, phosphorus initial concentration are 5,10,20,40,60,80, background ions KNO in solution3Concentration 5 mmol/L, pH be 4.5 ±
0.2, biological hybrid material dosage is 0.5g/L, concussion reaction 24 hours at 25 DEG C.The results show that with the increasing of initial concentration
The adsorption capacity of composite material is added also to gradually increase, 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 has selenite radical, arsenate, phosphate radical
Stronger processing capacity.By taking selenite radical as an example, material can be further investigated to the place of selenite radical by column adsorption experiment
Reason ability.Steps are as follows for specific experiment: prepare simulation waste water containing selenite radical: initial selenium concentration is 1mg/L, NO3 ‒、Cl‒、SO4 2‒
Content is respectively 20,20,10mg/L, and raw water pH is 6 ± 0.2, and biomass composite dosage is 10 mL, flow velocity 15-
30min/BV, under the premise of being discharged selenium concentration lower than 0.1 mg/L, difference quaternary ammonium group made from technique produced according to the present invention
The biomass combined adsorbent of content and different iron contents is 95-2200BV to the treating capacity of selenium.
As shown in Figure 1, gradually increasing with the increase of iron content in biological hybrid material to the adsorbance of selenite radical
Add, when iron load capacity reaches 18%, selenate radical adsorbance reaches maximum.When iron load capacity continues growing, adsorbance is in decline
Trend causes adsorption site to block this is because iron load capacity is excessively high, so as to cause adsorbance reduction.In view of adsorption effect with
Preparation cost, carrying the best iron load capacity of iron biology hybrid material is 18%.
Embodiment 15
It, can from embodiment 2,5,9,11 it can be seen that carrying lanthanum biology hybrid material has stronger processing capacity to phosphate radical
Material is further investigated to the processing capacity of phosphate radical by column adsorption experiment.Steps are as follows for specific experiment: preparing simulation and contains
Phosphorus waste water: phosphorus concentration 5mg/L, NO3 ‒、Cl‒、SO4 2‒Content is respectively 50,50,25mg/L, and raw water pH is 5 ± 0.2, hydridization
Material utilization amount is that 5mL, flow velocity 15-30min/BV make according to the present invention under the premise of being discharged phosphorus concentration lower than 0.5mg/L
The lanthanum hybrid material that carries of difference quaternary ammonium group content made from standby technique and different lanthanum contents is 150-5800 to the treating capacity of phosphorus
BV。
As shown in Fig. 2, the adsorbance of phosphate radical is gradually increased with the increase of lanthanum content in biological hybrid material,
When lanthanum load capacity reaches 15%, Phosphateadsorption amount reaches maximum.When lanthanum load capacity continues growing, adsorbance becomes in decline
Gesture causes adsorption site to block this is because lanthanum load capacity is excessively high, so as to cause adsorbance reduction.In view of adsorption effect and system
Standby cost, the load capacity for carrying the best lanthanum of lanthanum biology hybrid material is 15%.
Embodiment 16
From embodiment 3,6,10,13 it can be seen that carry zirconium biology hybrid material to phosphate radical, arsenate have it is stronger from
Reason ability.By taking arsenate as an example, material can further be investigated to arsenate by column adsorption experiment by carrying zirconium biology hybrid material
Processing capacity.Steps are as follows for specific experiment: preparing simulation waste water containing arsenate: arsenic concentration 3mg/L, NO3 ‒、Cl‒、SO4 2‒Contain
Amount is respectively 50,50,100mg/L, and raw water pH is 4.5 ± 0.2, and biomass composite dosage is 7.5mL, flow velocity 15-
30min/BV, under the premise of being discharged phosphorus concentration lower than 0.5mg/L, difference quaternary ammonium group made from technique produced according to the present invention
The biomass combined adsorbent of content and different zirconium contents is 80-3200 BV to the treating capacity of arsenate.
As shown in figure 3, the adsorbance of arsenate is gradually increased with the increase of zirconium content in biological hybrid material,
When zirconium load capacity reaches 19%, Arsenate adsorption amount reaches maximum.When zirconium load capacity continues growing, adsorbance becomes in decline
Gesture causes adsorption site to block this is because zirconium load capacity is excessively high, so as to cause adsorbance reduction.In view of adsorption effect and system
Standby cost, the load capacity for carrying the best zirconium of zirconium biology hybrid material is 19%.
Claims (7)
1. a kind of quaternary ammonium salt of selective absorption phosphorus, arsenic, selenium/oxide modifying biology hybrid material preparation method, feature
Be: the biology hybrid material uses the chloro- 2- Hydroxyproyl Trimethyl ammonium chloride of 3- to be changed for etherifying agent using stalk as raw material
Property, quaternary ammonium salt-modified anionic biology exchanger is prepared；Then in its area load metal oxide to get described
Quaternary ammonium salt/oxide modifying biology hybrid material；The metal oxide is iron oxide, lanthana or zirconium oxide；The metal
Oxide is nano-oxide particles；When the metal oxide is iron oxide, the load of iron on the biology hybrid material
Amount is 2-31 wt %；When the metal oxide is lanthana, the load capacity of lanthanum is 1-24 on the biology hybrid material
wt %；When the metal oxide is zirconium oxide, the load capacity of zirconium is 1-27 wt % on the biology hybrid material.
2. preparation method according to claim 1, it is characterised in that: the biology hybrid material is original with wheat stalk
Material, the load capacity of iron are 18%.
3. preparation method according to claim 1, it is characterised in that: the biology hybrid material is original with rice straw
Material, the load capacity of lanthanum are 15%.
4. preparation method according to claim 1, it is characterised in that: the biology hybrid material is original with corn stover
Material, the load capacity of zirconium are 19%.
5. preparation method according to claim 1, it is characterised in that: it is described biology hybrid material the preparation method is as follows:
(1) preparation of quaternary ammonium salt-modified anionic biology exchanger: take 2-30g agricultural crop straw particle and 20-600mL mixed
Bonding solvent mixing, is warming up to 50-120 DEG C；Then it is chloro- 10-150mL 3- to be dropped evenly with the speed of 2-60mL/min thereto
2- Hydroxyproyl Trimethyl ammonium chloride is stirred to react 0.5-8 hours at 50-120 DEG C；After reaction, it filters, wash product
To neutrality, 25-80 DEG C vacuum drying 2-24 hours, obtain quaternary ammonium salt-modified anionic biology exchanger；The mixing is molten
Agent uses organic solvent to be mixed with NaOH aqueous solution with volume ratio 0.1:1-10:1, and organic solvent uses methanol, isopropanol
Or ethyl alcohol, the concentration of NaOH aqueous solution are 1-50%；
(2) metal oxide supported: to take the chlorate of 2-100g metal or nitrate or zirconium oxychloride that 10-500mL HCl is added
Aqueous solution prepares mixed solution, adds the above-mentioned biological exchanger of 1-20g, 25-80 DEG C is stirred to react 1-12 hours；Reaction terminates
Afterwards, strainer filters out, and filter residue material is added in 10-500mL NaOH aqueous solution, and 25-80 DEG C is stirred to react 1-12 hours；Instead
After answering, product is washed to neutrality, is then successively washed with the NaCl solution of 5-30wt%, deionized water, 25-80 DEG C true
Sky dries 2-24 hours to get quaternary ammonium salt/oxide modifying biology hybrid material is arrived；The metal selects iron or lanthanum；The HCl
The concentration of aqueous solution is 0.1-1mol/L；The concentration of the NaOH aqueous solution is 2-30wt%.
6. preparation method according to claim 5, it is characterised in that: the agricultural crop straw particle selection wheat stalk,
Mixture more than rice straw, cotton stalk, corn stover, soybean stalk, cassava stalk or both；The agricultural crop straw
The particle size of particle is 0.2-1.5mm.
7. preparation method according to claim 5, it is characterised in that: mixed solvent uses organic in the step (1)
Solvent is isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611004077.1A CN106492765B (en) | 2016-11-15 | 2016-11-15 | A kind of preparation method of quaternary ammonium salt/oxide modifying biology hybrid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611004077.1A CN106492765B (en) | 2016-11-15 | 2016-11-15 | A kind of preparation method of quaternary ammonium salt/oxide modifying biology hybrid material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106492765A CN106492765A (en) | 2017-03-15 |
| CN106492765B true CN106492765B (en) | 2019-03-08 |
Family
ID=58324576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611004077.1A Active CN106492765B (en) | 2016-11-15 | 2016-11-15 | A kind of preparation method of quaternary ammonium salt/oxide modifying biology hybrid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106492765B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570122A (en) * | 2017-10-12 | 2018-01-12 | 南京信息工程大学 | A kind of difunctional hybrid material of biomass and preparation method and application |
| CN110026159A (en) * | 2019-04-29 | 2019-07-19 | 广西科技师范学院 | A kind of preparation method of lead adsorbent |
| CN115672282A (en) * | 2022-10-13 | 2023-02-03 | 青岛科技大学 | Preparation method of simple and reproducible biogas residue-based anion adsorbent |
| CN115957724B (en) * | 2023-03-17 | 2023-06-06 | 农业农村部环境保护科研监测所 | Preparation method and application of quaternary ammonium modified straw |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752280A (en) * | 2014-01-07 | 2014-04-30 | 河海大学 | Composite modified walnut shell adsorbent as well as preparation method and application of composite modified walnut shell absorbent |
| CN104353440A (en) * | 2014-11-28 | 2015-02-18 | 南京信息工程大学 | Biomass resin based inorganic nano-oxide composite adsorbent and preparation method and application thereof |
| CN105214629A (en) * | 2015-10-30 | 2016-01-06 | 南京信息工程大学 | A kind of biomass-based nano lanthanum oxide dephosphorization compound adsorbent and preparation method thereof |
| CN105776481A (en) * | 2016-03-16 | 2016-07-20 | 江阴职业技术学院 | Xanthate cation dual-modified straw fiber printing and dyeing wastewater treatment agent and preparation method thereof |
-
2016
- 2016-11-15 CN CN201611004077.1A patent/CN106492765B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752280A (en) * | 2014-01-07 | 2014-04-30 | 河海大学 | Composite modified walnut shell adsorbent as well as preparation method and application of composite modified walnut shell absorbent |
| CN104353440A (en) * | 2014-11-28 | 2015-02-18 | 南京信息工程大学 | Biomass resin based inorganic nano-oxide composite adsorbent and preparation method and application thereof |
| CN105214629A (en) * | 2015-10-30 | 2016-01-06 | 南京信息工程大学 | A kind of biomass-based nano lanthanum oxide dephosphorization compound adsorbent and preparation method thereof |
| CN105776481A (en) * | 2016-03-16 | 2016-07-20 | 江阴职业技术学院 | Xanthate cation dual-modified straw fiber printing and dyeing wastewater treatment agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 季铵阳离子纤维素醚的合成;赵耀明等;《华南理工大学学报》;20070831;第83-88页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106492765A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106492765B (en) | A kind of preparation method of quaternary ammonium salt/oxide modifying biology hybrid material | |
| CN106215978B (en) | Organic-inorganic hybrid mesoporous catalyst and preparation method thereof for purifying VOCs | |
| CN105107467B (en) | One kind utilizes preparation of rear modification MIL 101 (Cr) adsorbent and application thereof | |
| CN106268701B (en) | A kind of resin base composite absorbent and preparation method removing phosphorus and fluorine in water removal for synchronizing depth | |
| CN104226259B (en) | A kind of threonine modified attapulgite earth adsorbing and application thereof | |
| CN105727903B (en) | A kind of modified porous diatomaceous preparation method of dimethyl diallyl ammonium chloride | |
| CN105149011B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN105617979B (en) | A kind of modified mesoporous silicon oxide adsorbent and the preparation method and application thereof | |
| CN103071463A (en) | Modified peanut shell Pb(II) adsorbent, and preparation method and application thereof | |
| CN105617981A (en) | Sepiolite modification method and application of modified sepiolite to wastewater treatment | |
| CN106179247A (en) | A kind of Cr VI adsorbent and its preparation method and application | |
| CN111110843A (en) | Preparation method and antibacterial application of photosensitive semiconductor Zr-TCPP MOFs (zirconium-tungsten-propylene-silicon) load Ag nano particle composite material | |
| CN106824069B (en) | For handling the preparation method of the rear-earth-doped iron Carbon Materials of arsenic-containing waste water | |
| CN106824096A (en) | One step hydro thermal method prepares functional amido Carbon Materials adsorbent | |
| CN106268652A (en) | A kind of preparation method of heavy metal chelating agent based on MOFs | |
| CN102614851A (en) | Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater | |
| CN109078602B (en) | Magnetic microporous lithium adsorbent and preparation method and application thereof | |
| CN106943995A (en) | A kind of modified clinoptilolite and preparation method and remove waste water in Pb ions application | |
| CN109395697A (en) | A kind of preparation method carrying silver-colored adsorbent and its application in water body containing iodine | |
| CN108435134A (en) | The preparation and its application of egg white-graphene oxide self-assembled compound material | |
| CN106955677A (en) | It is a kind of based on ion liquid modified egg shell/acticarbon and preparation method thereof | |
| CN107029674A (en) | A kind of rare earth modified medical stone and peanut shell composite adsorbing material and preparation method thereof | |
| CN106732345A (en) | A kind of composite adsorbing material for heavy metal containing wastewater treatment and preparation method thereof | |
| CN107176649B (en) | Method for separating 2-naphthalenesulfonic acid in wastewater by using iron-loaded copper macroporous resin | |
| CN106140095B (en) | The modified preparation and application of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CB03 | Change of inventor or designer information |
Inventor after: Qiu Hui Inventor after: Liang Chen Inventor after: Qin Zhifeng Inventor after: Liu Lele Inventor after: Dai Haiyang Inventor after: Zhu Tian Inventor after: Bao Xinying Inventor before: Liu Lele Inventor before: Qiu Hui Inventor before: Liang Chen Inventor before: Liu Gang Inventor before: Qin Zhifeng Inventor before: Dai Haiyang Inventor before: Zhu Tian Inventor before: Bao Xinying |
|
| COR | Change of bibliographic data | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230427 Address after: 256600 Xinhai Industrial Park, Wudi County, Binzhou City, Shandong Province Patentee after: Shandong Xinguang Chemical Co.,Ltd. Address before: 210044 No. 219, Ning six road, Nanjing, Jiangsu Patentee before: Nanjing University of Information Science and Technology |