CN102500335B - Preparation method for biomass organic adsorption material based on modified glucose or cane sugar - Google Patents
Preparation method for biomass organic adsorption material based on modified glucose or cane sugar Download PDFInfo
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Abstract
The invention discloses a preparation method for a biomass organic adsorption material based on modified glucose or cane sugar. The preparation method is characterized by comprising the following steps of: mixing 10 to 40 mass parts of phthalic anhydride and 50 to 100 mass parts of organic solvent acetone; adding 5 to 20 mass parts of glucose and 2 to 20 mass parts of catalyst and mixing; heating the mixed materials to 60 to 100 DEG C; reacting with stirring at the temperature of between 60 and 100 DEG C for 6 to 12 hours to obtain a mixture after the reaction, wherein the catalyst is triethylamine or pyridine; cooling the mixture obtained after the reaction to room temperature; filtering; drying the filtrate by using inorganic salt magnesium sulfate; and distilling to remove the organic solvent to prepare the product. The prepared biomass organic adsorption material based on the modified glucose or cane sugar can be directly used for treating waste water containing heavy metal ions, has a good adsorption effect on the heavy metal ions in the waste water and high practicability, and is low in cost.
Description
Technical field
The invention belongs to as the glucose of sorbing material or the chemical modification material preparation of sucrose, relate to a kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose.The living beings organic adsorption material based on modified glucose or sucrose that makes is specially adapted to the adsorption cleaning of heavy metal ions in wastewater and processes.
Background technology
Heavy metal (such as copper, zinc, lead, nickel, cobalt, chromium, mercury, cadmium etc.) is indispensable important materials in many industrial production and scientific research, and they are in the mankind's life and play a part very important in producing.But these heavy metal ion also have great harm to the mankind's life and ecological environment.The waste residue, waste gas, the waste water that contain heavy metal ion mainly come from the industries such as plating, machining, iron and steel and non-ferrous metal metallurgy, part chemical enterprise and mining." three wastes " that contain heavy metal are directly entered in the large G﹠W, will directly cause great threat to ecological environment and human health.
Heavy metal not only can cause slow poisoning, and can also be carcinogenic, mutagenesis, teratogenesis, its toxic is larger.A lot of heavy metal wastewater therebies are water white, misss to make the water that cleans and be directly used in and drink and irrigate.Heavy metal element toxicity is large, and difficult degradation in case just can directly act on human body by drinking water or domestic water after entering water body, greatly endangers artificial one-tenth.Heavy metal pollution has become one of important pollution problem that water environment faces.Heavy metal has bioconcentration
,They can not be biodegradable, and but can shift step by step along food chain, and are rich long-pending at double, simultaneously in biological internal organ long-term accumulation, toxicity occurs after acquiring a certain degree; What is more, and the radioactive component that is rich in can cause biological gene to morph, and finally can cause the disastrous effects difficult to the appraisal such as biological sudden change along with the accumulation of time.Environment is in a single day contaminated by heavy metals, and the difficulty of improvement is very large, and the cycle is also very long, and method and the technology of administering at present heavy metal pollution are ripe not enough, and therefore, heavy metal pollution should be to put prevention first.Need to from waste water, remove or reclaim the Another reason of heavy metal ion, be because some heavy metal expensive, have technique importance or have strategic importance, thereby have higher recycling and be worth.
Current, still perfect not to the treatment technology of heavy metal pollution both at home and abroad, far can not reach the degree that environment and organism are safe from harm.In the prior art, the method for processing heavy metal pollution mainly contains chemical method, physical-chemical process and bioanalysis, but these methods all can not make heavy metal wherein decompose destruction, the position that only can shift its existence.Process such as chemical precipitation, the heavy metal in the waste water changes insoluble chemical compound into and precipitates and change over to the mud from the ionic condition of dissolving; When also having amphoteric metal in the waste water, the pH value is higher, and the again tendency of dissolving might be arranged; If the higher need of the pH value of waste water behind the neutralization precipitation could discharge after neutralization; Some heavy metal particles is little, and difficult precipitation will be passed through other means aids precipitation, and these shortcomings have all increased difficulty and cost that heavy metal is processed.Absorption method is one of effective ways that reclaim micro heavy in the waste water, have the advantages such as wide accommodation, good, the recyclable useful heavy metal for the treatment of effect and sorbing material be reusable, existing sorbing material comprises mineral matter, inorganic salts, active carbon, synthetic resin etc.Domestic and international widely used adsorbent is active carbon, and is little to heavy metal ion adsorbed capacity although active carbon can adsorb many chemical substances, generally only has 30-40mg/g, and regeneration difficulty, expensive.The ion exchange resin adsorption capacity is higher, but only some specific adion is had adsorption capacity, and the regeneration difficulty, and price is high.The low price of natural zeolite and clay, but counterweight metal biosorption capacity is low, is generally less than 10mg/g.For this reason, many researchers are devoted to the research and development of novel absorption material, in recent years the natural biological material are used for the existing many researchs reports of absorption of aqueous systems heavy metal, but the adsorption capacity of these materials is strong or the problem such as commercial Application defectiveness.
Dextrose plus saccharose all can obtain by photosynthesis of plant at occurring in nature, has wide material sources, the advantage such as cheap.Glucose is the widest and of paramount importance a kind of monose of distributed in nature, and it is a kind of polyhydroxy aldehyde, has critical role in field of biology, is energy source and the metabolic intermediate product of living cells.Sucrose not only becomes additive important in the food with the not available characteristic of chemical synthesis sweetener, and because sucrose has unique function, is conducive to the processing of food and the raising of quality.Dextrose plus saccharose has a wide range of applications in industries such as food, medicine, chemical industry, cosmetics, washing agent.Dextrose plus saccharose is as the sufficient natural resources in source, but because of its functional group and characteristic such as biodegradable with chemical modification, is subject to paying close attention to more and more widely at antineoplastic and surfactant field.
Summary of the invention
Purpose of the present invention is intended to overcome deficiency of the prior art, a kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose is provided, is directly used in that heavy metal ion-containing waste water is processed, the respond well living beings organic adsorption material based on modified glucose or sucrose thereby provide a kind of.
Content of the present invention is: the preparation method based on the living beings organic adsorption material of modified glucose or sucrose is characterized in that comprising the following steps:
A, raw material hybrid reaction: get phthalic anhydride 10～40 mass parts, mix with the organic solvent-acetone of 50～100 mass parts, make phthalic anhydride fully dissolve (dispersion) in organic solvent-acetone, add again the glucose of 5～20 mass parts, the catalyst mix of adding 2～20 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 6～12 hours, obtain reacting rear mixture;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is through inorganic salts dried over mgso (can be at room temperature dry 10～30min, with the water that generates except dereaction), again after organic solvent is removed in distillation (vapo(u)rizing temperature determines that according to the organic solvent of selecting purpose is to remove organic solvent), namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
In the content of the present invention: phthalic anhydride described in the step a can replace with chlorobenzoyl chloride, 4-nitro phthalic anhydride, the amino phthalic anhydride of 4-, benzyl chloride or P-methoxybenzoic acid.
In the content of the present invention: glucose described in the step a can replace with sucrose.
In the content of the present invention: organic solvent-acetone described in the step a can replace with the tert-butyl alcohol, pyridine or DMF.
In the content of the present invention: the mass percentage content that catalyst described in the step a can replace with sulfuric acid is the aqueous sulfuric acid more than 90%.
In the content of the present invention: described step b post processing can replace with: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is after organic solvent and water are removed in distillation, namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
In the content of the present invention: in the described step b post processing, filtrate after organic solvent and water are removed in distillation, remaining material can also be again through washing purifying (when particularly selecting sulfuric acid to make catalyst), drying etc., with the living beings organic adsorption material of the high end product of acquisition purity based on modified glucose or sucrose.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) adopts the present invention, dextrose plus saccharose is by the chemical modification process, in the molecule of dextrose plus saccharose, introduced elements (containing lone pair electrons or free electron) such as containing aerobic, nitrogen and had the fragrance derivatives of coordination ability, the complexing power of itself and heavy metal ion is strengthened greatly; The products therefrom dissolubility is good, can dissolve in the common organic solvents such as acetone, ethanol, and their adsorption capacity and adsorption site are more, therefore, can be directly used in the purified treatment of heavy metal ion-containing waste water;
(2) adopt the present invention, by the biomass-based sorbing material with metal complex ability of the preparation take dextrose plus saccharose as matrix modification, acetyl group, the conjugation introduced at its molecule
Have certain complexing power after the system etc., and then possess the adsorption capacity to the Trace Components in the effluent containing heavy metal ions; This material also possesses good desorption and regeneration performance, can repeatedly reuse in the industrial application process, to reduce the cost of wastewater treatment, realizes simultaneously the high efficiente callback recycling to heavy metal ion; Can complete biodegradable after this sorbing material product uses, environmentally safe can be widely used in the heavy metal ion that machinery manufacturing industry, chemical industry, Electroplating Operations, nuclear industry etc. produce and adsorb and separate; Material after its absorption is processed through an amount of, be easy to form the biomass-based compound of the three-dimensional net structure of porous, this compound is in gas storage and catch industry huge potentiality are arranged;
(3) product preparation process of the present invention is simple, and the raw materials such as dextrose plus saccharose are cheap and easy to get, and cost is low, is used for the processing, respond well, practical of heavy metal ion-containing waste water.
The specific embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose, comprise the following steps: 15 parts of (mass parts, unit can be kilogram, afterwards together) phthalic anhydride is dissolved under stirring condition in 100 parts of acetone, take by weighing 10 parts of glucose, gradation joins in the acetone soln, adds to add 3 parts of triethylamines in the backward solution of glucose as catalyst, and remaining glucose again gradation adds mixing; Reaction temperature is risen to 70 ℃, and stirring reaction naturally cooled to room temperature after 8 hours; The gained mixed material is filtered, obtain end product behind filtrate drying, the distillation purifying.
Embodiment 2:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose, comprise the following steps: 10 parts of (mass parts, unit can be kilogram, afterwards together) phthalic anhydride is dissolved under stirring condition in 100 parts of acetone, take by weighing 10 portions of sucrose, gradation joins in the acetone soln, adds to add 8 parts of triethylamines in the backward solution of sucrose as catalyst, and remaining sucrose again gradation adds mixing; Reaction temperature is risen to 70 ℃, and stirring reaction naturally cooled to room temperature after 8 hours.The gained mixed material is filtered, obtain end product behind filtrate drying, the distillation purifying.
Embodiment 3:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose, comprise the following steps: 12 parts of (mass parts, unit can be kilogram, afterwards together) phthalic anhydride joins to stir in 100 parts of tert-butyl alcohols under stirring condition and makes it be uniformly dispersed into solution, take by weighing 10 parts of glucose, gradation joins in the solution, adds to add 5 parts of triethylamines in the backward solution of glucose as catalyst, and remaining glucose again gradation adds mixing; Reaction temperature is risen to 95 ℃, and stirring reaction naturally cooled to room temperature after 8 hours; The gained mixed material is filtered, obtain end product behind filtrate drying, the distillation purifying.
Embodiment 4:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose comprises the following steps:
A, raw material hybrid reaction: (unit can be kilogram to get phthalic anhydride 10 mass parts, together rear), mix with the organic solvent-acetone of 50 mass parts, make phthalic anhydride fully dissolve (dispersion) in organic solvent-acetone, add again the glucose of 5 mass parts, the catalyst mix of adding 2 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 6 hours, obtain reacting rear mixture;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is through inorganic salts dried over mgso (can be at room temperature dry 10～30min, with the water that generates except dereaction), again after organic solvent is removed in distillation (vapo(u)rizing temperature determines that according to the organic solvent of selecting purpose is to remove organic solvent), namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
Embodiment 5:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose comprises the following steps:
A, raw material hybrid reaction: (unit can be kilogram to get phthalic anhydride 40 mass parts, together rear), mix with the organic solvent-acetone of 100 mass parts, make phthalic anhydride fully dissolve (dispersion) in organic solvent-acetone, add again the glucose of 20 mass parts, the catalyst mix of adding 20 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 12 hours, obtain reacting rear mixture;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is through inorganic salts dried over mgso (can be at room temperature dry 10～30min, with the water that generates except dereaction), again after organic solvent is removed in distillation (vapo(u)rizing temperature determines that according to the organic solvent of selecting purpose is to remove organic solvent), namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
Embodiment 6:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose comprises the following steps:
A, raw material hybrid reaction: (unit can be kilogram to get phthalic anhydride 25 mass parts, together rear), mix with the organic solvent-acetone of 75 mass parts, make phthalic anhydride fully dissolve (dispersion) in organic solvent-acetone, add again the glucose of 12 mass parts, the catalyst mix of adding 11 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 8 hours, obtain reacting rear mixture;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is through inorganic salts dried over mgso (can be at room temperature dry 10～30min, with the water that generates except dereaction), again after organic solvent is removed in distillation (vapo(u)rizing temperature determines that according to the organic solvent of selecting purpose is to remove organic solvent), namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
Embodiment 7:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose comprises the following steps:
A, raw material hybrid reaction: (unit can be kilogram to get phthalic anhydride 10～40 mass parts, together rear), mix with the organic solvent-acetone of 50～100 mass parts, make phthalic anhydride fully dissolve (dispersion) in organic solvent-acetone, add again the glucose of 5～20 mass parts, the catalyst mix of adding 2～20 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 6～12 hours, obtain reacting rear mixture;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is through inorganic salts dried over mgso (can be at room temperature dry 10～30min, with the water that generates except dereaction), again after organic solvent is removed in distillation (vapo(u)rizing temperature determines that according to the organic solvent of selecting purpose is to remove organic solvent), namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
Embodiment 8-14:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose comprises the following steps:
A, raw material hybrid reaction: (unit can be kilogram to get phthalic anhydride 10～40 mass parts, together rear), mix with the organic solvent-acetone of 50～100 mass parts, make phthalic anhydride fully dissolve (dispersion) in organic solvent-acetone, add again the glucose of 5～20 mass parts, the catalyst mix of adding 2～20 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 6～12 hours, obtain reacting rear mixture; The concrete consumption of each component raw material sees the following form 1 among each embodiment;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is through inorganic salts dried over mgso (can be at room temperature dry 10～30min, with the water that generates except dereaction), again after organic solvent is removed in distillation (vapo(u)rizing temperature determines that according to the organic solvent of selecting purpose is to remove organic solvent), namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
Table 1: the concrete scale of using of each component raw material among each embodiment:
Embodiment 15:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose, phthalic anhydride described in the step a replaces with chlorobenzoyl chloride, 4-nitro phthalic anhydride, the amino phthalic anhydride of 4-, benzyl chloride or P-methoxybenzoic acid; Arbitrary in the other the same as in Example 1-14, slightly.
Embodiment 16:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose, glucose replaces with sucrose described in the step a; Arbitrary in the other the same as in Example 1-15, slightly.
Embodiment 17:
A kind of preparation method of the living beings organic adsorption material based on modified glucose or sucrose, the mass percentage content that catalyst described in the step a replaces with sulfuric acid are the aqueous sulfuric acid more than 90%; Arbitrary in the other the same as in Example 1-16, slightly.
In above-described embodiment: organic solvent-acetone described in the step a can replace with the tert-butyl alcohol, pyridine or DMF.
In above-described embodiment: described step b post processing can replace with: after mixture is cooled to room temperature after will reacting, filter, discard solids, filtrate is after organic solvent and water are removed in distillation, namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
In above-described embodiment: in the described step b post processing, filtrate after organic solvent and water are removed in distillation, remaining material can also be again through washing purifying (when particularly selecting sulfuric acid to make catalyst), drying etc., with the living beings organic adsorption material of the high end product of acquisition purity based on modified glucose or sucrose.
In above-described embodiment: each raw material that adopts is the commercially available prod, wherein:
In above-described embodiment: in the percentage that adopts, do not indicate especially, be weight (quality) percentage; Described quality (weight) part can all be gram or kilogram.
In above-described embodiment: the technological parameter in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, content of the present invention is described all can implement and have described good result.
Claims (6)
1. based on the preparation method of the living beings organic adsorption material of modified glucose or sucrose, it is characterized in that comprising the following steps:
A, raw material hybrid reaction: get phthalic anhydride 10～40 mass parts, mix with the organic solvent-acetone of 50～100 mass parts, the catalyst mix that adds again the glucose of 5～20 mass parts or sucrose, adding 2～20 mass parts, with mixed material be warming up to 60～100 ℃ and under this temperature stirring reaction 6～12 hours, obtain reacting rear mixture;
Described catalyst is triethylamine or pyridine;
B, post processing: after mixture will be cooled to room temperature after will reacting, filter, filtrate is through the inorganic salts dried over mgso, again after organic solvent is removed in distillation, namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
2. by the preparation method of the living beings organic adsorption material based on modified glucose or sucrose claimed in claim 1, it is characterized in that: phthalic anhydride described in the step a replaces with chlorobenzoyl chloride, 4-nitro phthalic anhydride, the amino phthalic anhydride of 4-, benzyl chloride or P-methoxybenzoic acid.
3. by the preparation method of claim 1 or 2 described living beings organic adsorption materials based on modified glucose or sucrose, it is characterized in that: organic solvent-acetone described in the step a replaces with the tert-butyl alcohol, pyridine or DMF.
4. by the preparation method of claim 1 or 2 described living beings organic adsorption materials based on modified glucose or sucrose, it is characterized in that: the mass percentage content that catalyst described in the step a replaces with sulfuric acid is the aqueous sulfuric acid more than 90%.
5. by the preparation method of claim 1 or 2 described living beings organic adsorption materials based on modified glucose or sucrose, it is characterized in that: described step b post processing replaces with: after mixture is cooled to room temperature after will reacting, filter, filtrate is after organic solvent and water are removed in distillation, namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
6. by the preparation method of the living beings organic adsorption material based on modified glucose or sucrose claimed in claim 3, it is characterized in that: described step b post processing replaces with: after mixture is cooled to room temperature after will reacting, filter, filtrate is after organic solvent and water are removed in distillation, namely make product based on the living beings organic adsorption material of modified glucose or sucrose.
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| CN101269318A (en) * | 2008-04-28 | 2008-09-24 | 江汉大学 | Metallic ion adsorption material and preparation method thereof |
| CN101759809A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing dithiocarbamate-based modified porous starch |
| CN102160993A (en) * | 2011-04-29 | 2011-08-24 | 西南科技大学 | Thermoplastic deacetylated glucomannan blending adsorption material and preparation method thereof |
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| JPH10113675A (en) * | 1996-10-09 | 1998-05-06 | Kokichi Sakai | Trapping agent for heavy metal and trapping method of heavy metal |
| FR2885125B1 (en) * | 2005-04-28 | 2007-11-09 | Rhodia Chimie Sa | USE OF POLYSACCHARIDES FOR REMOVING HEAVY METALS IN THE FORM OF ANIONS IN WATER |
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| CN101269318A (en) * | 2008-04-28 | 2008-09-24 | 江汉大学 | Metallic ion adsorption material and preparation method thereof |
| CN101759809A (en) * | 2010-01-14 | 2010-06-30 | 同济大学 | Method for preparing dithiocarbamate-based modified porous starch |
| CN102160993A (en) * | 2011-04-29 | 2011-08-24 | 西南科技大学 | Thermoplastic deacetylated glucomannan blending adsorption material and preparation method thereof |
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