CN103464118B - A kind of preparations and applicatio of epoxychloropropane palm fibre modification palmitic acid bark adsorbent - Google Patents
A kind of preparations and applicatio of epoxychloropropane palm fibre modification palmitic acid bark adsorbent Download PDFInfo
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- CN103464118B CN103464118B CN201310443587.9A CN201310443587A CN103464118B CN 103464118 B CN103464118 B CN 103464118B CN 201310443587 A CN201310443587 A CN 201310443587A CN 103464118 B CN103464118 B CN 103464118B
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Abstract
The invention discloses a kind of epoxychloropropane modified palm bark adsorbent preparation method and application technology, feature is: palm bark washed with water and remove earth and impurity, dry, pulverizing, after isopropyl alcohol and NaOH aqueous solution process drying, obtain alkalization palm bark, in the reactor, add by following composition mass percent, epoxychloropropane: 20 ~ 35%, alkalization palm bark: 6 ~ 20%, NaOH:2 ~ 8%; Water: 40 ~ 60%, each component sum is absolutely, in 40 ~ 50 DEG C of constant temperature, stirring, back flow reaction 0.5 ~ 2h, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, be placed in 45 ~ 55 DEG C of vacuum drying chambers dry, obtain epoxychloropropane modified palm bark, this adsorbent has very high adsorption capacity to basic-dyeable fibre, excellent physical chemistry and mechanical performance, the strong Reusability of power of regeneration, the not only low but also environmental protection of cost.
Description
Technical field
The present invention relates to a kind of preparation method of biological adsorption agent and the applied technical field to Dye Adsorption in industrial wastewater, particularly the epoxychloropropane modified palm bark adsorbent preparation method of one and application technology.
Background technology
Palm is perennial aiphyllium plant, Gao Keda 7 meters; Dry upright, not branch, the palm-bark rain cape formed by leaf sheath is wrapped; Therefore very long, the intensity of the fiber of palm bark is large, is typically used as making mattress, and being one of most valuable ecological resources, is a kind of renewable resource.Current palm extensively plants area on the south the Changjiang river, is very precious long fibered raw material.This natural macromolecular material application makes absorption and has the features such as natural, green, biodegradable, mechanical strength is large, resistance to corrosion is strong, palm bark is reused repeatedly as adsorbent is renewable, and have larger adsorption capacity to dyestuff, little abroad to the research report of palm bark chemical modification and absorption property, Chinese Patent Application No. is: the preparation method and the application that disclose a kind of sulfydryl palm bark adsorbent in the patent of 201310147720.6.
Along with the fast development of industry, the consumption of dyestuff is also increasing, and synthetic dyestuffs, compared with natural dye, have the advantage such as easy to use, stable in properties, cost are low, wide in variety and are widely used in weaving, papermaking, pharmacy and food industry.Waste water from dyestuff has become China's at present one of main pollutant effluents, and solving problem of environmental pollution is very urgent problems.The structure of current most of synthetic dyestuffs has complicated aromatic ring structure, and character is very stable, is difficult to biodegradation.These dyestuffs can threaten to the health of the mankind, enter food chain, may cause the allergy of people, the various injuries such as the sudden change of cancer and gene.What the widely using of dyestuff caused dye wastewater is discharged in natural water in a large number, cause water pollution, even if a small amount of waste water from dyestuff discharge also can cause water body painted, the heavy damage natural, ecological chain of water body, also greatly reduces the economic worth of water body simultaneously.Therefore, the dyestuff how removed in industrial wastewater is the focus of domestic and international experts and scholars research.In the industrial production, waste water from dyestuff adopts flocculence, oxidizing process, biological treatment, membrane filter method, absorption method etc. usually.Wherein absorption method has technique simply, and adsorption rate is high, applied widely, and the features such as stable in properties are used widely in sewage disposal.
Since the nineties in 20th century, people utilize natural fiber cheap and easy to get in the process of waste water from dyestuff, to obtain more research as adsorbent.Neha Gupta etc. have studied methylene blue in potato stalk adsorbed water and malachite green, its maximum adsorption capacity is: 52.6mg/g, (Neha Gupta, Application of potato (Solanum tuberosum) plant wastes for the removal of methylene blue and malachite green dye from aqueous solution. Arabian Journal of Chemistry, (2011)); Runping Han etc. have studied the fallen leaves of Chinese parasol tree tree to the methylene blue adsorption number in water, its maximum adsorption capacity is: 89.7mg/g, (Runping Han, Biosorption of methylene blue from aqueous solution by fallen phoenix tree ' s leaves. Journal of Hazardous Materials, 141 (2007) 156 – 162); Li Shan etc., have studied methylene blue in epoxychloropropane modified peanut shell adsorbed water, it to the maximum adsorption capacity of methyl blue is: 25mg/g, (Li Shan etc., the research of methylene blue in epoxychloropropane modified peanut shell adsorbed water, dyestuff and dyeing, 2008,45(2): 49 ~ 51); Deng Jun is strong, have studied the absorption property that bagasse centering is red, and the red maximum adsorption capacity of its centering is: 27.10mg/g, (Deng Junqiang etc., the research of the experiment of the absorption property that bagasse centering is red, water science and engineering technology, 2012(5), 24 ~ 28).Natural macromolecular material is utilized as adsorbent and has the advantages such as renewable, degradable, environmental protection be friendly, cheap, is important living resources.
Summary of the invention
An object of the present invention is to provide a kind of epoxychloropropane modified palm bark adsorbent preparation method, mainly makes the epoxychloropropane modified palm bark adsorbent of acquisition larger as the adsorption capacity of the adsorbent of dyestuff in aqueous systems.
Object of the present invention is achieved through the following technical solutions.
A kind of epoxychloropropane modified palm bark adsorbent preparation method, is characterised in that the method has following processing step:
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 24 ~ 48 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark by 50 ~ 100g/L solid-to-liquid ratio, with the mixed solution that the NaOH solution of isopropyl alcohol and 0.2 ~ 1.0mol/L is 1:4 ~ 10 by volume, soaking at room temperature 12 ~ 20h, boil 15 ~ 40nim, deionized water is spent to neutral after cooling, suction filtration, 70 ~ 85 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane palm bark preparation: in the reactor, adds by following composition mass percent, epoxychloropropane: 20 ~ 35%, alkalization palm bark: 6 ~ 20%, NaOH:2 ~ 8%; Water: 40 ~ 60%, each component sum is absolutely, in 40 ~ 50 DEG C of constant temperature, stirring, back flow reaction 0.5 ~ 2 h, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, be placed in 45 ~ 55 DEG C of vacuum drying chambers dry, obtain epoxychloropropane modified palm bark.
Another object of the present invention is to provide a kind of epoxychloropropane palm bark adsorbent to basic-dyeable fibre absorption in aqueous systems, and feature is: the epoxychloropropane modified palm bark adsorbent deionized water prepared is soaked 1 ~ 2 h, adsorbs by static method.
The epoxychloropropane modified palm bark adsorbent deionized water prepared is soaked 1 ~ 2 h, adsorbs by dynamic method.
Advantage of the present invention and effect are:
(1) the epoxychloropropane modified palm bark adsorbent that the present invention obtains has good physical and chemical stability and excellent mechanical strength, large with modification tangerine peel, modified bamboo is considered to be worth doing, broomcorn straw compares dyestuff adsorption capacity, Reusability number of times improves greatly, can improve 1 times;
(2) the epoxychloropropane modified palm bark adsorbent that the present invention obtains can reach 146.8mg/g, 175.9mg/g, 149.2mg/g, 162.2mg/g respectively to the adsorption capacity of methylene blue, crystal violet, basic fuchsin and malachite green, reaches as high as 98.5% to the clearance of dyestuff in sewage; Can directly to absorption and the wash-out of basic-dyeable fibre various in water body, adsorption efficiency is high, and the speed of absorption is fast, and desorption performance is good, can use within the scope of wider soda acid;
(3) present invention process is simple, and condition is easy to control, and production cost is low, is easy to suitability for industrialized production;
(4) palm bark that the present invention uses is natural regeneration macromolecular material, with epoxychloropropane modified, uses this adsorbent environmentally safe, the advantages such as production cost is low, and discarded object is biodegradable.
Accompanying drawing explanation
Fig. 1 is the raw-material ESEM of palm bark (SEM) figure
Fig. 2 is ESEM (SEM) figure of epoxychloropropane palm bark.
Detailed description of the invention
Embodiment 1
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 30 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark 10g, with the 0.5mol/L NaOH mixed solution soaking at room temperature 15h of 40mL isopropyl alcohol and 160mL, boil 30nim, spend deionized water after cooling to neutral, after suction filtration, 70 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane modified palm bark preparation: in the reactor, add epoxychloropropane respectively: 20mL, alkalization palm bark: 15g, NaOH:2g; Water: 50mL, at 45 DEG C, constant temperature, stirring, back flow reaction 1 h, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, is placed in 50 DEG C of vacuum drying chambers dry, obtains epoxychloropropane modified palm bark.
Embodiment 2
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 24 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark 20g, with the 1.0mol/L NaOH mixed solution soaking at room temperature 20h of 50mL isopropyl alcohol and 200mL, boil 15nim, spend deionized water after cooling to neutral, after suction filtration, 70 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane modified palm bark preparation: in the reactor, add epoxychloropropane respectively: 25mL, alkalization palm bark: 10g, NaOH:2g; Water: 40mL, constant temperature, stirring, back flow reaction 0.5h at 50 DEG C, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, is placed in 55 DEG C of vacuum drying chambers dry, obtains epoxychloropropane modified palm bark.
Embodiment 3
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 30 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark 10g, with the 0.8mol/L NaOH mixed solution soaking at room temperature 20h of 20mL isopropyl alcohol and 180mL, boil 20nim, spend deionized water after cooling to neutral, after suction filtration, 75 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane modified palm bark preparation: in the reactor, add epoxychloropropane respectively: 25mL, alkalization palm bark: 5g, NaOH:3g; Water: 40mL, constant temperature, stirring, back flow reaction 2h at 40 DEG C, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, is placed in 50 DEG C of vacuum drying chambers dry, obtains epoxychloropropane modified palm bark.
Embodiment 4
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 48 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark 20g, with the 0.8mol/L NaOH mixed solution soaking at room temperature 15h of 20mL isopropyl alcohol and 180mL, boil 40nim, spend deionized water after cooling to neutral, after suction filtration, 70 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane modified palm bark preparation: in the reactor, add epoxychloropropane respectively: 30mL, alkalization palm bark: 20g, NaOH:6g; Water: 44mL, constant temperature, stirring, back flow reaction 1h at 45 DEG C, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, is placed in 50 DEG C of vacuum drying chambers dry, obtains epoxychloropropane modified palm bark.
Embodiment 5
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 30 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark 20g, with the 0.8mol/L NaOH mixed solution soaking at room temperature 12h of 50mL isopropyl alcohol and 350mL, boil 20nim, spend deionized water after cooling to neutral, after suction filtration, 70 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane modified palm bark preparation: in the reactor, add epoxychloropropane respectively: 22mL, alkalization palm bark: 10g, NaOH:8g; Water: 60mL, constant temperature, stirring, back flow reaction 1.5h at 50 DEG C, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, is placed in 55 DEG C of vacuum drying chambers dry, obtains epoxychloropropane modified palm bark.
Embodiment 6
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 48 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark 50g, with the 0.5mol/L NaOH mixed solution soaking at room temperature 15h of 50mL isopropyl alcohol and 450mL, boil 40nim, spend deionized water after cooling to neutral, after suction filtration, 70 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane modified palm bark preparation: in the reactor, add epoxychloropropane respectively: 10mL, alkalization palm bark: 5g, NaOH:2g; Water: 20mL, constant temperature, stirring, back flow reaction 0.5h at 50 DEG C, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, is placed in 55 DEG C of vacuum drying chambers dry, obtains epoxychloropropane modified palm bark.
Embodiment 7
Take the epoxychloropropane modified palm bark adsorbent of 0.50g and be placed in 250mL tool plug conical flask, adding 100mL concentration is in 550mg/L dye solution, be in 4.5 ~ 8.5 scopes with acid or the pH value of alkali regulation system, at room temperature shake absorption 0.5 ~ 1.5 h, get supernatant, by the concentration of spectrophotometric determination dyestuff, according to the concentration difference of dyestuff in water before and after absorption, calculate the adsorption capacity of epoxychloropropane modified palm bark adsorbent, the adsorption capacity result of the epoxychloropropane modified palm bark adsorbent obtained by embodiment 1 ~ 6 to dyestuff lists table 1. in
The epoxychloropropane modified palm bark adsorbent of table 1 is to the adsorption capacity measurement result of dyestuff
| Adsorbent title | pH | Adsorption time (h) | Methylene blue (mg/g) | Crystal violet (mg/g) | Basic fuchsin (mg/g) | Malachite green (mg/g) |
| Embodiment 1 | 4.5 | 0.5 | 145.2 | 174.2 | 148.2 | 160.8 |
| Embodiment 1 | 6.0 | 1.0 | 144.8 | 173.9 | 147.9 | 161.2 |
| Embodiment 2 | 7.0 | 1.5 | 143.2 | 174.5 | 148.5 | 160.5 |
| Embodiment 2 | 8.0 | 1.0 | 142.9 | 172.8 | 146.8 | 161.1 |
| Embodiment 3 | 5.0 | 1.5 | 146.5 | 175.1 | 147.5 | 161.8 |
| Embodiment 3 | 5.5 | 0.5 | 146.8 | 175.9 | 149.2 | 162.2 |
| Embodiment 4 | 6.5 | 1.5 | 145.1 | 174.5 | 147.2 | 159.9 |
| Embodiment 4 | 7.5 | 0.5 | 143.9 | 173.8 | 146.8 | 160.8 |
| Embodiment 5 | 5.5 | 1.2 | 146.5 | 175.7 | 149.1 | 162.1 |
| Embodiment 5 | 8.5 | 1 | 142.5 | 173.7 | 147.8 | 160.2 |
| Embodiment 6 | 5.8 | 1.5 | 145.9 | 175.8 | 148.9 | 161.4 |
| Embodiment 6 | 5.5 | 1 | 146.5 | 175.6 | 149.2 | 162.2 |
PH value adsorbent absorption on dyestuff in 4.5 ~ 8.5 scopes does not affect as seen from Table 1, at room temperature concussion absorption more than 0.5h, dyestuff adsorbs completely substantially, and the adsorption capacity of methylene blue, crystal violet, basic fuchsin and malachite green can reach 146.8mg/g, 175.9mg/g, 149.2mg/g, 162.2mg/g respectively.
Embodiment 8
Take the epoxychloropropane modified palm bark adsorbent of 1.0g and be placed in 250mL tool plug conical flask, adding 100mL concentration is in 200mg/L dye solution, be in 5.5 scopes with acid or the pH value of alkali regulation system, at room temperature shake absorption 1 h, get supernatant, by the concentration of spectrophotometric determination dyestuff, according to the concentration difference of dyestuff in water before and after absorption, calculate the clearance of epoxychloropropane modified palm bark adsorbent to dyestuff, the clearance result of epoxychloropropane modified palm bark adsorbent obtained by embodiment 1 ~ 6 to dyestuff lists this adsorbent of table 2. in methylene blue, crystal violet, basic fuchsin and malachite green four kinds of dyestuffs going in water processes all more than 95%, reach as high as 98.5%%.
The epoxychloropropane modified palm bark adsorbent of table 2 is to the clearance of dyestuff
| Adsorbent title | Methylene blue (%) | Crystal violet (%) | Basic fuchsin (%) | Malachite green (%) |
| Embodiment 1 | 97.6 | 97.8 | 95.6 | 95.9 |
| Embodiment 2 | 96.5 | 98.2 | 96.6 | 96.4 |
| Embodiment 3 | 98.5 | 97.5 | 98.1 | 97.2 |
| Embodiment 4 | 98.2 | 98.3 | 98.5 | 98.5 |
| Embodiment 5 | 98.5 | 97.5 | 97.6 | 98.1 |
| Embodiment 6 | 97.1 | 98.1 | 98.1 | 95.9 |
Claims (2)
1. an epoxychloropropane modified palm bark adsorbent preparation method, is characterized in that, the method has following processing step:
(1) palm bark pretreatment: palm bark be cut into small pieces, washes with water and removes earth and impurity, put into container and be soaked in water 24 ~ 48 hours, pulverize, obtain pretreatment palm bark after vacuum drying;
(2) alkalize palm bark: by pretreatment palm bark by 50 ~ 100g/L solid-to-liquid ratio, with the mixed solution that the NaOH solution of isopropyl alcohol and 0.2 ~ 1.0mol/L is 1:4 ~ 10 by volume, soaking at room temperature 12 ~ 20h, boil 15 ~ 40min, deionized water is spent to neutral after cooling, suction filtration, 70 ~ 85 DEG C of oven dry, obtain alkalization palm bark;
(3) epoxychloropropane palm bark preparation: in the reactor, adds by following composition mass percent, epoxychloropropane: 20 ~ 35%, alkalization palm bark: 6 ~ 20%, NaOH:2 ~ 8%; Water: 40 ~ 60%, each component sum is absolutely, in 40 ~ 50 DEG C of constant temperature, stirring, back flow reaction 0.5 ~ 2h, after cooling, spend deionized water, suction filtration, to filtrate is neutrality, after a small amount of ethanol washing, be placed in 45 ~ 55 DEG C of vacuum drying chambers dry, obtain epoxychloropropane modified palm bark.
2. the adsorbent prepared by the preparation method of a kind of epoxychloropropane modified palm bark adsorbent described in claim 1, is characterized in that, epoxychloropropane modified palm bark adsorbent is used for the absorption of the basic-dyeable fibre in water.
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| CN106268675B (en) * | 2016-09-07 | 2018-01-16 | 济南大学 | A kind of preparation of triethylene tetramine modified magnetic palm bark adsorbent |
| CN107233863B (en) * | 2017-06-23 | 2019-08-09 | 河北省廊坊水文水资源勘测局 | Iron, cadmium, arsenic ion adsorbent and preparation method thereof in a kind of water |
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| JPS59225739A (en) * | 1983-06-06 | 1984-12-18 | Japan Metals & Chem Co Ltd | Fumic acid type adsorbent |
| CN103191702A (en) * | 2013-04-26 | 2013-07-10 | 济南大学 | Preparation method and application of sulfydryl palm bark adsorbent |
| CN103212378A (en) * | 2013-04-26 | 2013-07-24 | 济南大学 | Preparation method and application of citric acid modified palm tree bark adsorbing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS59225739A (en) * | 1983-06-06 | 1984-12-18 | Japan Metals & Chem Co Ltd | Fumic acid type adsorbent |
| CN103191702A (en) * | 2013-04-26 | 2013-07-10 | 济南大学 | Preparation method and application of sulfydryl palm bark adsorbent |
| CN103212378A (en) * | 2013-04-26 | 2013-07-24 | 济南大学 | Preparation method and application of citric acid modified palm tree bark adsorbing agent |
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| 改性木屑吸附剂对印染废水的脱色性能研究;徐博函等;《中国环保产业》;20071231(第12期);第34-35页 * |
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