CN101070673A - Cellulose-base chelated fiber and its synthesizing method and use - Google Patents
Cellulose-base chelated fiber and its synthesizing method and use Download PDFInfo
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- CN101070673A CN101070673A CN 200710022977 CN200710022977A CN101070673A CN 101070673 A CN101070673 A CN 101070673A CN 200710022977 CN200710022977 CN 200710022977 CN 200710022977 A CN200710022977 A CN 200710022977A CN 101070673 A CN101070673 A CN 101070673A
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Abstract
This invention discloses a cellulose base chelated textile fiber and the synthetic method and the application. The chelated textile fiber takes the native cellulose textile fiber as the raw material. Through the duplet bond and the shrinkage glycerin compound carries on the free radical stem grafting copolymerization, we obtain the cellulose textile fiber which the epoxy activates, this epoxy activates the cellulose textile fiber and the polyethylene multi-amines respond a lot the amine chelated textile fiber, the multi-amine chelated textile fiber continues with the chloroacetic acid to respond, multi-amine multi-carboxylic acid chelated textile fiber. This kind of cellulose base chelated textile fiber has the fine trapping performance to the harmful heavy metal ion, and the synthetic method is simple, safe. the synthesis cost is low, too.
Description
One, the technical field
The invention belongs to the field of chemical modification of cellulose fiber, and particularly relates to cellulose-based chelate fiber as well as a synthesis method and application thereof. The cellulose-based chelate fiber can selectively and efficiently adsorb trace metal ions in water, particularly harmful heavy metal ions such ascopper, zinc and the like, and can be widely and effectively applied to purification of industrial wastewater, drinking water and the like.
Second, background Art
With the continuous development of industrial technology, water pollution becomes increasingly serious. The industrial waste water and drinking water contain various harmful heavy metal ions which must be removed, and simultaneously, the heavy metal ions can be separated and recovered, thereby changing waste into valuable.
Ion exchange resins and chelating resins are widely used for removing, trapping and enriching harmful metal ions in wastewater, but do not necessarily have good selectivity for metal ions with trace concentration.
Synthetic chelate resins in the form of particles generally have a rigid three-dimensional structure and high hydrophobicity, and the diffusion rate of metal ions or a regenerant into the resin is low, which affects the treatment efficiency, and particularly, it is difficult to incinerate the resin which is not regenerated but used once, and therefore, how to recover the adsorption capacity of the used resin is also a great problem.
The fibrous chelate resin has a large specific surface area, a high diffusion rate of metal ions or a regenerant into the fibers, high adsorption and desorption properties, and easy regeneration, and can be processed into various shapes, such as paper, net, etc., by placing the cellulose-based chelate fiber in a filter case to serve as a filter element.
In addition, the chelate fiber synthesized by using cellulose as a skeleton has biodegradability.
Third, the invention
Themain purposes of the invention are as follows: providing a cellulose-based chelating fiber; to provide a method for synthesizing a cellulose-based chelate fiber simply and safely; and a method for efficiently and selectively capturing harmful heavy metal ions, particularly in waste water and drinking water, by using the chelate fiber in a simple manner.
The purpose of the invention is realized by the following technical scheme:
a cellulose-based chelate fiber characterized by comprising an epoxy-activated cellulose fiber, a polyamine type chelate fiber and a polyamine polycarboxylic acid type chelate fiber. Wherein, the epoxy activated cellulose fiber is prepared by the mass ratio of the cellulose fiber to the compound containing double bonds and glycidyl groups of 1: 0.1-1: 4; the polyamine chelate fiber is prepared by mixing epoxy activated cellulose fiber and polyethylene polyamine in a mass ratio of 1: 1-1: 30; the polyamine polycarboxylic acid type chelate fiber is produced by mixing a polyamine type chelate fiber with chloroacetic acid in a mass ratio of 1: 0.5 to 1: 4.
The synthesis method of the cellulose-based chelate fiber is characterized in that free radical graft copolymerization is carried out on cellulose fiber and a compound containing double bonds and glycidyl groups to obtain epoxy activated cellulose fiber, the epoxy activated cellulose fiber is further reacted with polyethylene polyamine to obtain polyamine type chelate fiber, the polyamine type chelate fiber is continuously reacted with chloroacetic acid to obtain the polyamine polycarboxylic acid type chelate fiber, and the specific synthesis steps are as follows:
A. synthesis of epoxy activated cellulose fibers: carrying out graft copolymerization on cellulose fibers, a compound containing double bonds and glycidyl groups and a free radical polymerization catalyst in an aqueous medium according to the mass ratio of 1: 0.1: 0.05-1: 4: 0.2, wherein the reaction conditions are that the reaction is carried out for 5 minutes to 10 hours at the temperature of 40-95 ℃, filtering out the fibers after the reaction is finished, soaking the fibers in acetone or butanone at normal temperature for half an hour, and then carrying out Soxhlet extraction on the fibers for 24 hours by using the acetone or butanone;
B. synthesis of polyamine-type chelate fiber: reacting epoxy activated cellulose fiber and polyethylene polyamine in a mass ratio of 1: 1-1: 30 in any one or a mixture of any two or three of medium water, N-dimethylformamide and dimethyl sulfoxide at 40-95 ℃ for 10 minutes-10 hours, filtering out the fiber after the reaction is finished, and washing;
C. synthesis of polyamine polycarboxylic acid type chelate fiber: reacting polyamine chelate fiber with chloroacetic acid and potassium carbonate (or sodium hydroxide and potassium hydroxide) at the mass ratio of 1: 0.5: 0.3-1: 4: 2 at 50-80 ℃ for 0.5-20 hours, filtering out the fiber after the reaction is finished, and washing.
The cellulose-based chelate fiber of the present invention has a cellulose fiber skeleton, and specifically, is produced from grass (particularly preferably rice straw, reed, bagasse, devil's rush herb, bamboo), wood (particularly preferably eucalyptus, poplar, birch, masson pine, spruce), cotton, hemp and other agricultural and forestry wastes as raw materials by a chemical method, a mechanical method or a chemical-mechanical method, and can be used in combination with any of the fibers as required. Wherein the cellulose fiber prepared by the chemical method adopts one of soda pulping, sulfate pulp, bleached sulfate pulp, sulfite pulp and bleached sulfite pulp; the cellulose fiber prepared by the mechanical method adopts one of wood chip groundwood, groundwood and thermomechanical pulp; the cellulosefiber prepared by the chemical mechanical method adopts one of chemical thermomechanical pulp, alkaline hydrogen peroxide mechanical pulp chemically pretreated by disc grinding and bleaching chemical thermomechanical pulp. The shape of these cellulose fibers is not particularly limited, and these cellulose fibers can be used as they are, can be used by raising the surface of the fibers by mechanical action, can be used by grinding into powder, and can be used as a sheet or a fabric.
The double bond and glycidyl group-containing compound of the above step A is particularly preferably glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether, and these compounds may be used alone or in combination of two or three thereof as required.
The free radical polymerization catalyst in the step A is a high-valence metal ion catalyst or a redox catalyst; wherein the high valence metal ion catalyst is any one of high valence cerium salt, vanadium salt or potassium permanganate; wherein the redox catalyst is any one of ferrous salt, hydrogen peroxide, thiourea dioxide, ferrous salt, hydrogen peroxide, hydrazine or persulfate and ferrous salt.
The polyethylene polyamine in the step B is one or a mixture of more of ethylenediamine, butanediamine, hexanediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
In synthesizing the cellulose-based chelate fiber of the present invention, first, to obtain an epoxy-activated cellulose fiber as a reactive intermediate fiber, a compound having a double bond and a glycidyl group in the molecule is subjected to radical graft copolymerization to form a branched chain having an epoxy group in the skeleton of the cellulose fiber. Then, active epoxy groups on the cellulose fiber framework are utilized to introduce chelating functional groups. Therefore, it is very critical to use a compound containing a double bond and a glycidyl group, and glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether is particularly preferable for efficient graft copolymerization with cellulose fiber molecules and for efficient functionalization of the subsequent epoxy-activated cellulose fibers, and among these, glycidyl methacrylate is most preferable from the viewpoint of ease of introduction into the fiber molecules and availability of raw materials.
The first step of the method for synthesizing the cellulose-based chelate fiber is that the cellulose fiber and a compound containing double bonds and glycidyl groups are subjected to graft copolymerization in an aqueous phase in the presence of a free radical catalyst.
As the radical polymerization catalyst, a radical polymerization catalyst such as benzoyl peroxide or t-butyl hydroperoxide can be used alone, a high-valence metal ion catalyst such as a high-valence cerium salt, a vanadium salt or potassium permanganate can be used alone, or a redox catalyst can be used, and as the oxidizing agent, hydrogen peroxide or persulfate can be used, and as the reducing agent, a divalent iron salt, a divalent copper salt, thiourea dioxide, sulfite or hydrazine can be used. In order to efficiently carry out the graft copolymerization, it is preferable to use a higher cerium salt or a divalent iron salt in combination with hydrogen peroxide and thiourea dioxide or hydrazine.
In order to further improve the graft copolymerization of the cellulose fiber and the compound containing double bonds and glycidyl groups, the specific method is as follows:
1) a method of directly using cerium ammonium nitrate;
2) a method of using hydrogen peroxide and thiourea dioxide or hydrazine after treating cellulose fibers with a divalent iron salt in advance.
These methods are preferable because a desired graft polymerization reaction rate can be obtained even when the treatment is carried out under relatively mild conditions for a relatively short period of time.
The reaction for graft copolymerization directly initiated by cerium salt is exemplified as follows:
chain initiation
Chain growth
Chain termination
The generation of cellulose macro-molecular radicals when graft copolymerization is performed by a combination of a ferrous salt, hydrogen peroxide and thiourea dioxide is exemplified as follows:
H2O2+Fe2+→HO-+HO·+Fe3+
HO·+Cell-OH→H2O+Cell-O·
HO·+Fe2+→HO-+Fe3+
it can be seen that the addition of thiourea dioxide, which is a reducing component, can help to generate more free radicals, thereby helping to generate cellulose macromolecular free radicals.
The structure of the epoxy activated cellulose fiber obtained by graft copolymerization of glycidyl methacrylate and cellulose fiber is shown as the following formula:
a preferred method for graft copolymerization of cellulose fibers with compounds containing double bonds and glycidyl groups is as follows:
1) initiation system using ammonium ceric nitrate
Cellulose fibers are washed in advance, dehydrated to 20% -30% dryness and reacted at 40 ℃ -95 ℃ for 5 minutes to 10 hours in the presence of distilled water, cellulose fibers, a compound containing double bonds and glycidyl groups, an emulsifier and ammonium cerium nitrate.
2) Initiation system using ferrous salts, hydrogen peroxide and thiourea dioxide
The cellulose fiber is soaked in distilled water solution of ferrous salt at room temperature for 10-60 min while stirring, filtered, washed with distilled water and air dried. Reacting for 5 minutes to 10 hours at 40 ℃ to 95 ℃ in the presence of distilled water, air-dried cellulose fibers treated by ferrous salt, a compound containing double bonds and glycidyl groups, an emulsifier, hydrogen peroxide and thiourea dioxide.
According to these methods, a compound containing a double bond and a glycidyl group can be efficiently grafted onto a cellulose skeleton, thereby attaching an epoxy group having high reactivity to the cellulose skeleton. However, a certain grafting ratio and epoxy group content should be controlled. In the aspect of improving the trapping capacity of metal ions, the higher the grafting rate means that the active epoxy group content is high, and the active epoxy group content can react with more polyethylene polyamine, so that the chelating functional group content in the final product fiber is improved. However, too high a graft ratio affects the strength of the fiber and the effect of the fiber, and it is considered that the graft ratio is preferably controlled to 40% to 200%, more preferably 50% to 150%. The epoxy group content of the epoxy activated cellulose fiber is 0-4.4 mmol/g.
The polyethylene polyamine has high reactivity to epoxy groups and has chelating capacity to metal ions, so that polyamine chelating functional groups can be efficiently introduced into cellulose fibers bythe compound. In medium water or polar solvent such as N, N-dimethylformamide, dimethyl sulfoxide and the like, reaction medium is selected according to requirements to carry out reaction on polyethylene polyamine and epoxy activated cellulose fiber for 10 minutes to 10 hours at the temperature of 40 ℃ to 95 ℃, and then the polyamine type cellulose base chelate fiber is obtained. Specific reaction examples of epoxy-activated cellulosic fibers with a portion of polyethylene polyamine are as follows:
an example of the reaction of a portion of the polyamine-type chelate fibers with chloroacetic acid is as follows:
the polyamine polycarboxylic acid chelate fiber can be obtained by reacting the polyamine chelate fiber with chloroacetic acid and potassium carbonate (or sodium hydroxide and potassium hydroxide) at 50-80 ℃ for 0.5-20 hours.
The invention fully utilizes the natural substance of cellulose, which exists in the nature in large quantity, as the raw material to synthesize the cellulose-based chelate fiber. The successful synthesis of epoxy-activated cellulose fibers is among others the key to obtaining the final chelate fibers. The epoxy group content of the synthesized epoxy activated cellulose fiber is 0-4.4mmol/g, and the high epoxy group content ensures the further reaction with polyethylene polyamine.
The epoxy activated cellulose fiber reacts with polyethylene polyamine to obtain polyamine chelate fiber with nitrogen content of 0-8%. The polyamine polycarboxylic acid type chelate fiber is obtained after the polyamine type chelate fiber iscontinuously reacted with chloroacetic acid, the nitrogen content of the polyamine polycarboxylic acid type chelate fiber is 0-7%, and the carboxyl content of the polyamine polycarboxylic acid type chelate fiber is 0-5 mmol/g.
Particularly, the polyamine polycarboxylic acid type chelate fiber obtained by reacting ethylenediamine and diethylenetriamine with epoxy activated cellulose fiber and then continuing to react with chloroacetic acid has a structure extremely similar to that of common chelating agents of ethylenediamine tetraacetic acid and diethylenetriamine pentaacetic acid, and only one carboxymethyl group is reduced, so that the polyamine polycarboxylic acid type chelate fiber is called ED3A and DTTA type cellulose based chelate fiber, and the specific structure is shown as follows:
the use of fibrous chelating fibers for capturing metal ions in water can be carried out in a very simple manner. That is, cellulose-based chelate fibers are added to water containing metal ions, stirred, and then simply filtered to trap the metal ions in the water to be treated, thereby achieving a purification effect. The cellulose-based chelate fiber may be packed in a column or the like to pass a fluid to be treated, and this may also have the effect of trapping metal ions. Alternatively, the cellulose-based chelate fiber and the wet strength agent may be mixed with a predetermined amount of other fibers and then formed into a paper for use in a filter paper.
The cellulose-based chelate fiber obtained as described above may be used in the form of a fiber as it is, or may be processed into a sheet,a web or a filter. The chelating functional groups on the fiber surface have excellent selective adsorption performance on metal ions, and the target metal ions can be more effectively trapped by controlling the pH of the treated fluid.
Specifically, when the cellulose-based chelate fiber is placed directly in a liquid to be treated and stirred or packed in a column and the liquid or gas is passed through the fiber, the metal ions in the liquid or gas to be treated can be efficiently trapped or specific metal ions can be selectively trapped.
The fibers trapped with the metal ions are treated by a regenerant, so that the chelated metal ions can be simply separated, thereby recovering the metal ions in the liquid or gas to be treated, particularly valuable metal ions or metal ions with important specific application.
The synthesis method is simple and safe and has lower synthesis cost.
Description of the drawings
FIG. 1 is a graph showing the change with time of the amount of adsorption of copper ions in water by the polyamine type cellulose based chelate fiber and the polyamine polycarboxylic acid type cellulose based chelate fiber of the present invention. The two chelate fibers are synthesized by taking ferrous salt, hydrogen peroxide and thiourea dioxide as initiating systems and taking bleached sulfate eucalyptus pulp as a cellulose raw material.
Fifth, detailed description of the invention
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples, and can be carried out with appropriate modifications within a range suitable for the main contents described before and after, and all of these modifications are within the technical scope of the present invention.
Example 1
Preparing bleached sulfate eucalyptus pulp and glycidyl methacrylate into epoxy activated bleached sulfate eucalyptus pulp in a mass ratio of 1: 2; preparing polyamine bleached sulfate eucalyptus pulp from epoxy activated bleached sulfate eucalyptus pulp and ethylenediamine in a mass ratio of 1: 3.4; the polyamine type bleached sulfate eucalyptus pulp and chloroacetic acid are prepared into the polyamine polycarboxylic acid type bleached sulfate eucalyptus pulp in a mass ratio of 1: 2.
Example 2
Preparing epoxy activated masson pine thermomechanical pulp from masson pine thermomechanical pulp and glycidyl methacrylate in a mass ratio of 1: 1.5; preparing polyamine masson pine thermomechanical pulp from epoxy activated masson pine thermomechanical pulp and diethylenetriamine in a mass ratio of 1: 3; the polyamine type masson pine thermomechanical pulp and chloroacetic acid are prepared into the polyamine polycarboxylic acid type masson pine thermomechanical pulp in a mass ratio of 1: 1.
Example 3
Placing 2.5g of absolutely dry bleached sulfate eucalyptus pulp in 250ml of distilled water with nitrogen protection for uniform dispersion, adding 5.0g of glycidyl methacrylate, 0.2ml of emulsifier A and 10ml of 0.1mol/L cerium ammonium nitrate solution (prepared by 1mol/L nitric acid) for uniform dispersion, treating at 60 ℃ for 2 hours, filtering out fibers, soaking in butanone for 30 minutes at normal temperature, filtering, washing with hot distilled water, drying, and finally performing soxhlet extraction on butanone for 24 hours to obtain 4.8g of the bleached sulfate eucalyptus pulp grafted with glycidyl methacrylate.
1.0g of the obtained glycidyl methacrylate grafted bleached sulfate eucalyptus pulp was reacted with water, 3.8ml of ethylenediamine in N, N-dimethylformamide as a medium at 70 ℃ for 3 hours to obtain 1.12g of polyamine-type chelate fiber. 0.1g of the polyamine-type chelate fiber was added to 50ml of a copper nitrate and lead nitrate solution having a metal ion concentration of 500mg/L, respectively, the pH of the system was controlled to 5.0, and the system was shaken in a constant temperature shaker at 25 ℃ for 1 hour, whereby the adsorption amounts of copper ions and lead ions to the polyamine-type chelate fiber were measured to be 70mg/g and 211mg/g, respectively.
1.0g of the polyamine-type chelate fiber thus obtained was reacted with 2.0g of chloroacetic acid, 2.8g of potassium carbonate and water at 60 ℃ for 8 hours to obtain a polyaminopolycarboxylic acid-type chelate fiber. 0.1g of the polyamine polycarboxylic acid type chelate fiber was added to 100ml of a copper nitrate and lead nitrate solution having a metal ion concentration of 500mg/L, the pH of the system was controlled to 5.0, and the solution was shaken in a constant temperature shaker at 25 ℃ for 1 hour, whereby the adsorption amounts of copper ions and lead ions by the polyamine polycarboxylic acid type chelate fiber were found to be 106mg/g and 341mg/g, respectively.
Example 4
Soaking 5.0g of absolutely dry bleached sulfate eucalyptus pulp in 500ml of 0.04% ammonium ferrous sulfate solution at room temperature for 1 hour, filtering, washing, air-drying, then uniformly dispersing in 250ml of distilled water with nitrogen protection, adding 7.5g of glycidyl methacrylate, 0.2ml of emulsifier A, 0.5g of hydrogen peroxide and 0.1g of thiourea dioxide, treating at 70 ℃ for 4 hours, then filtering out fibers, soaking in butanone at room temperature for 30 minutes, filtering, washing with hot distilled water, drying, and finally performing soxhlet extraction with butanone for 24 hours to obtain 10.2g of glycidyl methacrylate grafted bleached sulfate eucalyptus pulp.
1.0g of the obtained glycidyl methacrylate-grafted bleached sulfate eucalyptus pulp was reacted with water, 3.8ml of ethylenediamine in N, N-dimethylformamide at 70 ℃ for 2 hours to obtain 1.16g of polyamine-type chelate fiber. The same adsorption experiment as in example 3 was carried out using the polyamine-type chelate fiber, and the adsorption amounts of copper ions and lead ions were measured to be 90mg/g and 289mg/g, respectively.
1.0g of the polyamine-type chelate fiber thus obtained was reacted with 2.0g of chloroacetic acid, 2.8g of potassium carbonate and water at 55 ℃ for 10 hours to obtain a polyaminopolycarboxylic acid-type chelate fiber. The same adsorption experiment as in example 3 was carried out on the polyamine polycarboxylic acid type chelate fiber, and the adsorption amounts of copper ions and lead ions were found to be 141mg/g and 432mg/g, respectively.
(copper ion adsorption Rate test)
In order to determine the adsorption rate of the polyamine-type chelate fiber and the polyamine-polycarboxylic acid-type chelate fiber obtained as described above with respect to copper ions, 0.1g of the chelate fiber was added to 50ml of a 500mg/L copper nitrate solution, and the change in the adsorption amount of copper ions with time was examined by controlling the system pH to 5.0. The results are shown in FIG. 1, and it is found that both the chelate fibers reach the saturated adsorption amount in a short time, and that the chelate fibers have an excellent adsorption/collection rate.
Example 5
Placing 2.5g of absolutely dry bleached sulfate eucalyptus pulp, 5.0g of glycidyl methacrylate, water and 0.2ml of emulsifier in a three-neck flask with nitrogen protection for uniform dispersion, then adding 0.2g of ferrous sulfate, starting to heat up, adding 0.7g of potassium persulfate when the temperature rises to 60 ℃, keeping the temperature at 60 ℃ for reaction for 3 hours, then filtering out fibers, soaking the fibers in acetone at normal temperature for 30 minutes, filtering, washing with hot distilled water, drying, and finally performing Soxhlet extraction on the fibers for 24 hours to obtain 3.9g of the bleached sulfate eucalyptus pulp grafted with glycidyl methacrylate.
1.0g of the obtained glycidyl methacrylate grafted bleached sulfate eucalyptus pulp is taken to react with water and 4.5ml of diethylenetriamine in an aqueous medium at 60 ℃ for 5 hours to obtain 1.07g of polyamine chelate fiber. The same adsorption experiment as in example 3 was carried out using the polyamine-type chelate fiber, and the adsorption amounts of copper ions and lead ions by the polyamine-type chelate fiber were measured to be 65mg/g and 209mg/g, respectively.
Example 6
The same procedure as in example 3 was repeated except that a wheat straw two stage oxygen Soda cooking (Soda-AQ/O2) pulp was used in place of the bleached kraft eucalyptus pulp in example 3 to obtain 3.8g of glycidyl methacrylate grafted wheat straw two stage oxygen Soda cooking pulp.
1.0g of the obtained glycidyl methacrylate grafted wheat straw two-stage oxygen alkali cooking pulp is taken to react with water and 4.1ml of triethylene tetramine in dimethyl sulfoxide at 70 ℃ for 3 hours to obtain 1.12g of polyamine chelate fiber. The same adsorption experiment as in example 3 was carried out using the polyamine-type chelate fiber, and the adsorption amounts of copper ions and lead ions by the polyamine-type chelate fiber weremeasured to be 61mg/g and 171mg/g, respectively.
1.0g of the polyamine-type chelate fiber thus obtained was reacted with 1.8g of chloroacetic acid, 1.2g of potassium carbonate and water at 60 ℃ for 8 hours to obtain a polyaminopolycarboxylic acid-type chelate fiber. The same adsorption experiment as in example 3 was carried out with respect to the polyamine polycarboxylic acid type chelate fiber, and the adsorption amounts of copper ions and lead ions by the polyamine polycarboxylic acid type chelate fiber were found to be 92mg/g and 256mg/g, respectively.
Example 7
9.2g of glycidyl methacrylate-grafted masson pine thermomechanical pulp was obtained in the same manner as in example 2, except that masson pine thermomechanical pulp was used instead of bleached kraft eucalyptus pulp in example 2.
1.0g of the obtained glycidyl methacrylate grafted masson pine thermomechanical pulp was reacted with water, 3.4ml of ethylenediamine in N, N-dimethylformamide at 70 ℃ for 6 hours to obtain polyamine type chelate fibers. The same adsorption experiment as in example 3 was carried out using the polyamine-type chelate fiber, and the adsorption amounts of copper ions and lead ions by the polyamine-type chelate fiber were found to be 75mg/g and 251mg/g, respectively.
1.0g of the polyamine-type chelate fiber thus obtained was reacted with 3.6g of chloroacetic acid, 2.8g of potassium carbonate and water at 60 ℃ for 6 hours to obtain a polyaminopolycarboxylic acid-type chelate fiber. The same adsorption experiment as in example 3 was carried out using the polyamine polycarboxylic acid type chelate fiber, and the adsorption amounts of copper ions and lead ions by the polyamine type chelate fiber were measured to be 112mg/g and 375mg/g, respectively.
Claims (10)
1. A cellulose-based chelate fiber comprising an epoxy-activated cellulose fiber, a polyamine-type chelate fiber and a polyamine-polycarboxylic acid-type chelate fiber, wherein the epoxy-activated cellulose fiber is prepared from a cellulose fiber and a compound containing a double bond and a glycidyl group in a mass ratio of 1: 0.1 to 1: 4; the polyamine chelate fiber is prepared by mixing epoxy activated cellulose fiber and polyethylene polyamine in a mass ratio of 1: 1-1: 30; the polyamine polycarboxylic acid type chelate fiber is produced by mixing a polyamine type chelate fiber with chloroacetic acid in a mass ratio of 1: 0.5 to 1: 4.
2. The cellulose-based chelate fiber according to claim 1, wherein the cellulose fiber is any one of cellulose fibers produced from grass, needle-leaved wood, hardwood, cotton, hemp, or agricultural and forestry waste; the cellulose fibers are produced by any of chemical, mechanical or chemimechanical processes.
3. The cellulose-based chelating fiber as set forth in claim 1, wherein the compound containing double bonds and glycidyl groups is any one of glycidyl methacrylate, glycidyl acrylate, or allyl glycidyl ether, or a mixture of any two or three thereof.
4. The cellulose-based chelate fiber according to claim 1, wherein the polyethylene polyamine is any one or a mixture of any two of ethylenediamine, butanediamine, hexanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
5. A synthetic method of cellulose-based chelate fiber is characterized in that the cellulose fiber and a compound containing double bonds and glycidyl are subjected to graft copolymerization underthe action of a free radical polymerization catalyst to obtain the epoxy activated cellulose fiber, the epoxy activated cellulose fiber is then reacted with polyethylene polyamine to obtain polyamine type chelate fiber, and the polyamine type chelate fiber is continuously reacted with chloroacetic acid to obtain the polyamine polycarboxylic acid type chelate fiber, wherein the specific synthetic steps are as follows:
A. synthesis of epoxy activated cellulose fibers: carrying out graft copolymerization on cellulose fibers, a compound containing double bonds and glycidyl groups and a free radical polymerization catalyst in an aqueous medium according to the mass ratio of 1: 0.1: 0.05-1: 4: 0.2, wherein the reaction conditions are that the reaction is carried out for 5 minutes to 10 hours at the temperature of 40-95 ℃, filtering out the fibers after the reaction is finished, soaking the fibers in acetone or butanone at normal temperature for half an hour, and then carrying out Soxhlet extraction on the fibers for 24 hours by using the acetone or butanone;
B. synthesis of polyamine-type chelate fiber: reacting epoxy activated cellulose fiber and polyethylene polyamine in a mass ratio of 1: 1-1: 30 in any one or a mixture of any two or three of medium water, N-dimethylformamide and dimethyl sulfoxide at 40-95 ℃ for 10 minutes-10 hours, filtering out the fiber after the reaction is finished, and washing;
C. synthesis of polyamine polycarboxylic acid type chelate fiber: reacting polyamine chelate fiber, chloroacetic acid and potassium carbonate or sodium hydroxide or potassium hydroxide at the mass ratio of 1: 0.5: 0.3-1: 4: 2 at 50-80 ℃ for 0.5-20 hours, filtering out the fiber after the reaction is finished, and washing.
6. The method of claim 5, wherein the radical polymerization catalyst in step A isa high valence metal ion catalyst or a redox catalyst.
7. The synthesis method according to claim 6, wherein the high valence metal ion catalyst is any one of high valence cerium salt, vanadium salt or potassium permanganate.
8. The method of claim 6, wherein the redox catalyst is any one of ferrous salt, hydrogen peroxide and thiourea dioxide, ferrous salt, hydrogen peroxide and hydrazine, or persulfate and ferrous salt.
9. The method of claim 8, wherein the cellulose fibers are pretreated with a ferrous salt and then subjected to a graft copolymerization reaction by the action of hydrogen peroxide and thiourea dioxide or hydrazine; or after the cellulose fiber is pretreated by persulfate, the graft copolymerization reaction is carried out by the action of ferrous salt.
10. Use of the cellulose-based chelating fibers as defined in claim 1 for removing, trapping, recovering metal ions, especially harmful heavy metal ions, in water or gas.
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