CN108118560B - Heavy metal ion filter paper and preparation method thereof - Google Patents

Heavy metal ion filter paper and preparation method thereof Download PDF

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Publication number
CN108118560B
CN108118560B CN201711386965.9A CN201711386965A CN108118560B CN 108118560 B CN108118560 B CN 108118560B CN 201711386965 A CN201711386965 A CN 201711386965A CN 108118560 B CN108118560 B CN 108118560B
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heavy metal
filter paper
pulp
metal ion
ion filter
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CN108118560A (en
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刘立华
刘思焱
薛建荣
赵露
唐安平
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Hunan University of Science and Technology
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Hunan University of Science and Technology
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/08—Filter paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/02—Methods of beating; Beaters of the Hollander type
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents

Abstract

The invention relates to heavy metal ion filter paper and a preparation method thereof. The wood pulp fiber is fully knocked down, devillicate and broomed in a beating machine; then, hydrolyzing the tetraethoxysilane to generate silicate radicals and combine with calcium ions under the alkaline condition by taking the calcium salt as a calcium source, tetraethoxysilane as a silicon source and wood pulp fiber as a support and a reaction site to generate calcium silicate in-situ loaded on the fiber; the filter paper is made, so that the filter paper has the capacity of adsorbing and intercepting heavy metal ions in wastewater, heavy metals in wastewater can be removed through common filtration, and the filter paper has wide popularization and application values.

Description

Heavy metal ion filter paper and preparation method thereof
Technical Field
The invention relates to the field of heavy metal wastewater treatment, in particular to heavy metal ion filter paper and a preparation method thereof.
Background
More and more heavy metal ions are released into the environment, which causes serious environmental pollution and harms the health of people. Heavy metal pollution has become one of the most problematic environmental problems worldwide. To reduce the harm of heavy metals, many efforts have been made to eliminate heavy metals. The adsorption method is one of the most commonly used treatment methods, and is popular in the water treatment field due to the advantages of simple treatment process, convenient operation, high treatment efficiency and suitability for deep treatment of low concentration, particularly wastewater. The adsorbent is the key to determining the effectiveness of the adsorption treatment. Due to the structural limitation of the activated carbon, the zeolite and the natural clay, the activated functional groups are few, and the adsorption capacity to heavy metals is generally small. The synthetic adsorption material can be designed according to the characteristics of an adsorption object and the adsorption treatment requirement, so that a good effect can be generally achieved, but the problems that the adsorption material is difficult to manufacture, the cost is high and the like often exist.
The search and research of a rapid and simple separation method of heavy metal ions are always the direction of efforts in the field of heavy metal wastewater treatment. The filtration is the most common suspended matter separation method, and has high separation efficiency, high speed and low cost. However, because the particle size of heavy metal ions is small, the radius of the hydrated ions is generally below 1nm, heavy metal ions cannot be intercepted by adopting common filtration, and heavy metal ions cannot be intercepted even by microfiltration, ultrafiltration and nanofiltration, so that a filter material (material) must be improved, or the forms of heavy metal ions are changed, for example, micelle-enhanced ultrafiltration and polymer-enhanced ultrafiltration are to increase the particle size of the heavy metal ions by adding a surfactant to wrap the heavy metal ions in micelles or fixing the heavy metal ions on a polymer through the polymer so as to facilitate the interception by an ultrafiltration membrane. The filter material is improved, on one hand, the size of filter pores is further reduced, and on the other hand, the adsorption and retention capacity of heavy metals is improved by modifying and loading active substances. By these measures, the separation of heavy metals can be made as easy as ordinary filtration.
Disclosure of Invention
Aiming at the problems of the adsorption method for treating the heavy metal wastewater and the filter material (material) used by the common filtering method, the invention provides the heavy metal ion filter paper which is made of wood pulp fiber with porous calcium silicate loaded on the surface, has the function of filtering and intercepting the heavy metal ions and is characterized in that: (1) under the existence of cellulose which is subjected to beating and high devillicate and brooming, porous calcium silicate with strong adsorption capacity to heavy metal ions is synthesized in situ, so that the calcium silicate is highly dispersed in the fiber by taking the cellulose as a template and relying and is firmly attached to the fiber, and the adsorption interception capacity and the stability to the heavy metal are improved; (2) the fiber loaded with porous calcium silicate is taken as a raw material, auxiliary materials such as a wet strength agent and the like are added, and the paper is made into filter paper for filtering heavy metal wastewater, so that the heavy metal can be separated simply and conveniently like common filtration; (3) has higher heavy metal interception capability and excellent wastewater permeability, can realize the synchronous separation of suspended matters and water-soluble heavy metal ions in the wastewater, and achieves the one-time purification of the treated water.
The invention also aims to provide a preparation method of the heavy metal ion filter paper, which comprises the following steps:
(1) adding water into wood pulp fibers to prepare pulp with the mass percentage concentration of 4.5-5.0%, pulping on a pulping machine, controlling the pulping time to be 4.5-5.5 h, wherein the light cutter is defibered for 1-1.5 h, the middle cutter is defibered for 2.5-3 h, the heavy cutter is defibered for 1-1.5 h, and the quality control indexes are as follows: the slurry hanging amount is 8.0-8.5 g, and the beating degree is 85-92 DEG SR;
(2) adding the slurry prepared in the step (1) into a reactor, adding water to dilute the slurry until the mass percentage of the fibers is 0.4-0.5%, fully stirring the slurry for 1-2 hours, then adding calcium salt according to the mass ratio of the calcium salt to the wood pulp fibers of 0.5-2.5: 1, continuously stirring the mixture for 1-1.5 hours after the calcium salt is dissolved, and then adding sodium hydroxide to adjust the pH value of the solution to 9.5-10.5; slowly dropwise adding tetraethoxysilane according to the mass ratio of tetraethoxysilane to calcium salt of 1.0-1.2: 1, continuously stirring and reacting for 2-4 hours after dropwise adding, standing and aging for 12-24 hours, filtering, and washing for 3-5 times by using water;
(3) adding water into the wood pulp loaded with the porous calcium silicate cleaned in the step (2) to prepare slurry with the mass percentage concentration of 1.0-1.5%, then adding a wet strength agent with the mass of 0.3-0.8% of that of the slurry, homogenizing, then using a rapid Kaithen (Kaithen) former to make sheets, and drying to obtain heavy metal ion filter paper; or homogenizing, making paper according to conventional paper making process, molding, squeezing, and drying to obtain heavy metal ion filter paper.
Further, in the step (1), the wood pulp is softwood pulp or hardwood pulp.
Further, the water in the steps (1) and (2) is clean tap water.
Further, in the step (2), the calcium salt is water-soluble calcium nitrate, calcium nitrate tetrahydrate, calcium chloride or calcium chloride hexahydrate.
Further, in the step (2), the sodium hydroxide is sodium hydroxide solid or sodium hydroxide solution.
Further, in the step (2), the ethyl orthosilicate is an industrial grade product with the mass fraction of 99.0%.
Further, in step (2), the reactor is equipped with a mechanical stirring and a constant pressure dropping funnel.
Further, in the step (3), the wood pulp loaded with the porous calcium silicate is softwood pulp loaded with the porous calcium silicate or/and hardwood pulp loaded with the porous calcium silicate, and when the wood pulp is the softwood pulp loaded with the porous calcium silicate and the hardwood pulp loaded with the porous calcium silicate, the mass ratio of the softwood pulp loaded with the porous calcium silicate to the hardwood pulp loaded with the porous calcium silicate is 5: 2-3.
Further, in the step (3), the wet strength agent is polyamine polyamide epichlorohydrin resin (PAE), and the mass fraction is 12.5 +/-0.5%.
Further, in the step (3), the model of the Kaithen former is HAD-KZCX-159/200A.
The invention relates to heavy metal ion filter paper and a preparation method thereof. The wood pulp fiber is fully knocked down, devillicate and broomed in a beating machine; then, hydrolyzing the tetraethoxysilane to generate silicate radicals and combine the silicate radicals with calcium ions under the alkaline condition by taking a calcium salt as a calcium source, tetraethoxysilane as a silicon source and wood pulp fiber as a support and a reaction site to generate calcium silicate in-situ loaded on cellulose; the obtained softwood pulp and hardwood pulp loaded with porous calcium silicate are mixed according to a certain proportion, wet strength agent is added, and paper making is carried out after homogenization to obtain filter paper, so that the defect that template agent is generally added or the synthesis is carried out under the ultrasonic condition for synthesizing porous calcium silicate is overcome, the generated calcium silicate can be highly dispersed and firmly combined on fibers, the stability of the cellulose loaded porous calcium silicate filter material is improved, and the filter paper prepared by paper making has the capacity of adsorbing and intercepting heavy metal ions in wastewater, and the aim of removing heavy metal in the wastewater by common filtration is fulfilled.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention loads porous calcium silicate with strong adsorption capacity to various heavy metal ions on cellulose and manufactures the porous calcium silicate into filter paper, and the filter paper has the function of adsorbing and intercepting the heavy metal ions in the wastewater, so that the heavy metal wastewater treatment is simple and convenient as common suspended matter filtration treatment. Therefore, the invention not only develops the treatment method of the heavy metal wastewater, but also expands the use method of the porous calcium silicate as a high-efficiency heavy metal wastewater treatment material, so that the porous calcium silicate has higher practicability in the heavy metal wastewater treatment.
(2) The method of the invention fully beats, devises and brooms the wood pulp fiber raw material through pulping, provides rich places for the synthesis and attachment of calcium silicate, plays a role of a template agent and promotes the generation and growth of calcium silicate. And because calcium silicate is produced and grown on the highly devillicate and broomed fibers, the loaded calcium silicate has not only good fusibility with the fibers, but also high stability.
(3) The product of the invention can be used as the filter paper of wastewater containing various heavy metal ions, and can remove insoluble suspended matters and soluble heavy metal ions in the wastewater in one step through filtering operation to achieve the purpose of purifying the heavy metal wastewater, so that the treatment process of the heavy metal wastewater can be simplified, and the invention has wide popularization and application values and application prospects.
(4) The preparation method has the advantages of simple process flow, mild operation conditions, easy control, no need of special or complex equipment, low investment and convenient popularization and industrialization.
The product of the invention is suitable for filtering treatment of various heavy metal wastewater.
Drawings
FIG. 1 is a block diagram of a process for preparing the present invention;
FIG. 2 is an infrared spectrum of hardwood pulp and its supported porous calcium silicate material obtained in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a softwood pulp loaded porous calcium silicate material according to example 1 of the present invention.
FIG. 4 is a scanning electron microscope image of hardwood pulp loaded porous calcium silicate material of example 1.
Detailed Description
The present invention is described in further detail below with reference to the attached drawing figures.
Example 1
(1) 150kg of softwood pulp is taken and added with water to prepare a slurry with the mass percentage concentration of 5.0%, and the slurry is pulped on a ZDC type pulping machine, and is defibered for 1.0h by a light knife, knocked for 3h by a medium knife and knocked for 1.5h by a heavy knife for 5.5 h. Measuring the hanging pulp amount to be 8.8g and the beating degree to be 90 DEG SR;
beating broad-leaved wood pulp under the same conditions, and determining the pulp hanging amount to be 9.0g and the beating degree to be 92 DEG SR;
(2) adding 100g of the softwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle, adding water to dilute the softwood pulp wet pulp until the mass percentage of the fibers is 0.4%, fully stirring the mixture for 2 hours, adding 10.15g of calcium nitrate tetrahydrate, stirring the mixture for dissolving, continuing stirring the mixture for 1.5 hours, and then adding solid NaOH to adjust the pH value to 10.1; slowly adding 10.85g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting for 4 hours at room temperature after dripping, and standing and aging for 24 hours; filtering, washing with distilled water for 5 times to obtain softwood pulp loaded porous calcium silicate wet pulp for later use; preparing hardwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with the porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 2, adding water to prepare slurry with the mass percentage concentration of 1.5%, then adding 33.6mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then using a rapid Kaithen (Kaithen) former to make sheets, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.562 g.
Infrared spectroscopic analysis was performed on samples of hardwood pulp and the resulting material of example 1, the results are shown in FIG. 2; scanning electron microscopy analysis of softwood pulp and hardwood pulp loaded porous calcium silicate in example 1 is shown in fig. 3 and 4, respectively.
In FIG. 2, the hardwood pulp infrared spectrum characteristic peaks can be assigned as follows: 3386.9cm-1The absorption peak is the stretching vibration absorption peak of-OH group in cellulose, 2894.7cm-1The absorption peak is ascribed to the C-H stretching vibration peak, 1635.6cm-1The absorption peak of (A) was assigned as the C ═ O stretching vibration peak, 1429.6cm-1Has an absorption peak of-CH2Peak of deformation vibration of 1369.7 and 1302.4cm-1Has an absorption peak of-CH3and-CH2Peak of flexural vibration, 1168.3 and 1036.6cm-1The absorption peak can be assigned as C-O stretching vibration peak, 784.1cm-1Is a ring-shaped C-O-C asymmetric out-of-plane stretching vibration peak of 6680.5-543.7 cm-1The absorption peak is-OH out-of-plane deformation vibration peak. Compared with hardwood pulp infrared spectrum, after the calcium silicate porous material is loaded, the corresponding absorption peak positions and peak intensities are changed and are also 1457.3, 982.8, 933.4, 785.7 and 468.5cm-1Etc. new absorption peaks appear, which can be assigned as follows: 1457.3cm-1Is SiO3 2-Characteristic absorption peak of (8), 982.8cm-1Is a stretching vibration peak of Si-OH and belongs to SiO4Characteristic peak of tetrahedron, 933.4cm-1Bending vibration peaks of O-H in Si-OH, 785.7 and 468.5cm-1Is the stretching vibration peak of Si-O-Si. These results all indicate that the porous calcium silicate has been supported on cellulose.
As can be seen from fig. 3 and 4, the fibers in the softwood pulp-supported porous calcium silicate are in a long linear shape, calcium silicate adheres to the surfaces of the fibers, hardwood pulp fibers are in a ribbon shape, and calcium silicate adheres to the surfaces or at the gaps where the devillicates cross. Both show that the porous calcium silicate has adhered firmly to the fibers.
The characterization results of the materials obtained in the rest of the examples are basically consistent.
Example 2
(1) 150kg of hardwood pulp is taken and added with water to prepare pulp with the mass percentage concentration of 4.5 percent, and the pulp is pulped on a ZDC type pulping machine, and is defibered for 1.5 hours by a light knife, is defibered for 2.5 hours by a medium knife, and is defibered for 1 hour by a heavy knife, and the total time is 5 hours. Measuring the hanging pulp amount to be 8.5g, and the beating degree to be 89 DEG SR;
the leaf wood pulp is beaten according to the same conditions, the measured pulp hanging amount is 8.3g, and the beating degree is 87 DEG SR;
(2) adding 112g of the hardwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the hardwood pulp wet pulp until the mass percentage of the fiber is 0.5%, fully stirring the hardwood pulp wet pulp for 1 hour, adding 5.10g of calcium nitrate tetrahydrate, stirring the hardwood pulp for dissolving, continuing stirring the hardwood pulp for 1 hour, and adding solid NaOH to adjust the pH value to 9.50; slowly adding 4.54g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting at room temperature for 3 hours after dripping, and standing and aging for 12 hours; filtering, washing with distilled water for 3 times to obtain hardwood pulp loaded porous calcium silicate wet pulp for later use; preparing softwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 3, adding water to prepare slurry with the mass percentage concentration of 1.2%, then adding 19.2mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then using a rapid Kaithen (Kaithen) former to make sheets, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.501 g.
Example 3
(1) 150kg of softwood pulp is taken and added with water to prepare a pulp with the mass percentage concentration of 4.75%, and the pulp is pulped on a ZDC type pulping machine, and is defibered for 1.0h by a light knife, for 2.5h by a medium knife and for 1.5h by a heavy knife, and for 5.0h in total. Measuring the hanging pulp amount to be 8.8g and the beating degree to be 90 DEG SR;
beating broad-leaved wood pulp according to the same conditions, measuring the pulp hanging amount to be 8.9g, and the beating degree to be 89 DEG SR;
(2) adding 105.3g of the softwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the softwood pulp wet pulp until the mass percentage of the fibers is 0.45%, fully stirring the mixture for 1.5h, adding 7.60g of calcium nitrate tetrahydrate, stirring the mixture for dissolving, continuing stirring the mixture for 1.5h, and then adding solid NaOH to adjust the pH value to 10.10; slowly adding 7.45g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting at room temperature for 3.5 hours after dripping, and standing and aging for 18 hours; filtering, washing with distilled water for 4 times to obtain softwood pulp loaded porous calcium silicate wet pulp for later use; preparing hardwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with the porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 2.5, adding water to prepare slurry with the mass percentage concentration of 1.0%, then adding 48.0mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then making sheets by using a rapid Kaithen (Kaithen) former, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.575 g.
Example 4
(1) 150kg of hardwood pulp is taken and added with water to prepare a sizing agent with the mass percentage concentration of 5.0 percent, and the hardwood pulp is pulped on a ZDC type pulping machine, and is defibered for 1.0h by a light knife, 2.5h by a medium knife and 1.5h by a heavy knife for 5.0 h. Measuring the hanging pulp amount to be 8.9g and the beating degree to be 91 DEG SR;
the leaf wood pulp is beaten according to the same conditions, the measured pulp hanging amount is 8.7g, and the beating degree is 88 DEG SR;
(2) adding 100g of the hardwood pulp wet pulp beaten in the step (1) into 1500mL of a three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the hardwood pulp wet pulp until the mass percentage of the fiber is 0.5%, fully stirring the hardwood pulp wet pulp for 1.25h, adding 7.06g of calcium nitrate, stirring the hardwood pulp for dissolving, continuing stirring the hardwood pulp for 1.5h, and adding solid NaOH to adjust the pH value to 10.50; slowly adding 9.96g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting at room temperature for 2.5h after dripping, and standing and aging for 20 h; filtering, washing with distilled water for 5 times to obtain hardwood pulp loaded porous calcium silicate wet pulp for later use; preparing softwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 2, adding water to prepare slurry with the mass percentage concentration of 1.5%, then adding 28.0mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then using a rapid Kaithen (Kaithen) former to make sheets, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.523 g.
Example 5
(1) 150kg of hardwood pulp is taken and added with water to prepare pulp with the mass percentage concentration of 4.5 percent, and the pulp is pulped on a ZDC type pulping machine, and the pulp is defibered for 1.0h by a light knife, is defibered for 3.0h by a medium knife, is defibered for 1.0h by a heavy knife, and is totally 5.5 h. Measuring the hanging pulp amount to be 8.5g and the beating degree to be 86 DEG SR;
the leaf wood pulp is beaten according to the same conditions, the measured pulp hanging amount is 8.2g, and the beating degree is 85 DEG SR;
(2) adding 112g of the hardwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the hardwood pulp wet pulp until the mass percentage of the fiber is 0.45 percent, fully stirring the hardwood pulp wet pulp for 1.5h, adding 3.53g of calcium nitrate, stirring the hardwood pulp for dissolving, continuing stirring the hardwood pulp for 1h, and adding solid NaOH to adjust the pH value to 9.5; slowly adding 4.53g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting at room temperature for 2 hours after dripping, and standing and aging for 12 hours; filtering, washing with distilled water for 3 times to obtain hardwood pulp loaded porous calcium silicate wet pulp for later use; preparing softwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with the porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 2.5, adding water to prepare slurry with the mass percentage concentration of 1.3%, then adding 36.0mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then using a rapid Kaithen (Kaithen) former to make sheets, and then placing the sheets in a drying box to dry to obtain heavy metal ion filter paper sheets with the mass of 2.495 g.
Example 6
(1) 150kg of softwood pulp is taken and added with water to prepare a pulp with the mass percentage concentration of 4.5%, and the pulp is pulped on a ZDC type pulping machine, and is defibered for 1.0h by a light knife, 2.5h by a medium knife and 1h by a heavy knife for 4.5 h. Measuring the hanging pulp amount to be 8.0g and the beating degree to be 85 DEG SR;
beating broad-leaved wood pulp under the same conditions, and determining the pulp hanging amount to be 8.4g and the beating degree to be 87 DEG SR;
(2) adding 112g of the softwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the softwood pulp wet pulp until the mass percentage of the fibers is 0.45%, fully stirring for 1h, adding 2.5g of calcium chloride, stirring and dissolving, continuing stirring for 1.5h, and then adding solid NaOH to adjust the pH value to 9.8; slowly adding 5.69g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting at room temperature for 3 hours after dripping, and standing and aging for 15 hours; filtering, washing with distilled water for 4 times to obtain softwood pulp loaded porous calcium silicate wet pulp for later use; preparing hardwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with the porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 2.8, adding water to prepare slurry with the mass percentage concentration of 1.2%, then adding 43.7mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then making sheets by using a rapid Kaithen (Kaithen) former, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.538 g.
Example 7
(1) 150kg of softwood pulp is taken, added with water to prepare a slurry with the mass percentage concentration of 5.0%, and then pulped on a ZDC type pulping machine, and the slurry is fluffed for 1.0h by a light knife, is fluffed for 3h by a medium knife and is fluffed for 1h by a heavy knife for 5 h. Measuring the hanging pulp amount to be 8.4g and the beating degree to be 87 DEG SR;
beating broad-leaved wood pulp under the same conditions, and determining the pulp hanging amount to be 8.7g and the beating degree to be 88 DEG SR;
(2) adding 100g of the softwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the softwood pulp wet pulp until the mass percentage of the fibers is 0.4%, fully stirring for 1.5h, adding 4.77g of calcium chloride, stirring and dissolving, continuing stirring for 1.5h, and then adding solid NaOH to adjust the pH value to 10.2; slowly adding 9.04g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting for 4 hours at room temperature after dripping, and standing and aging for 24 hours; filtering, washing with distilled water for 5 times to obtain softwood pulp loaded porous calcium silicate wet pulp for later use; preparing hardwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with the porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 2.2, adding water to prepare slurry with the mass percentage concentration of 1.0%, then adding 34.6mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then making sheets by using a rapid Kaithen (Kaithen) former, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.521 g.
Example 8
(1) 150kg of hardwood pulp is taken and added with water to prepare a sizing agent with the mass percentage concentration of 5.0 percent, and the hardwood pulp is pulped on a ZDC type pulping machine, and is defibered for 1.0h by a light knife, knocked for 3h by a medium knife and knocked for 1.5h by a heavy knife for 5.5 h. Measuring the hanging pulp amount to be 9.0g and the beating degree to be 91 DEG SR;
the leaf wood pulp is beaten according to the same conditions, the measured pulp hanging amount is 9.0g, and the beating degree is 88 DEG SR;
(2) adding 100g of the hardwood pulp wet pulp beaten in the step (1) into a 1500mL three-necked bottle provided with a constant-pressure dropping funnel and mechanical stirring, adding water to dilute the hardwood pulp wet pulp until the mass percentage of the fiber is 0.5%, fully stirring the hardwood pulp wet pulp for 2 hours, adding 7.5g of calcium chloride hexahydrate, stirring the hardwood pulp for dissolving, continuing stirring the hardwood pulp for 1.5 hours, and then adding solid NaOH to adjust the pH value to 9.9; slowly adding 7.92g of ethyl orthosilicate with the mass fraction of 99.0%, continuously reacting for 5 hours at room temperature after dripping, and standing and aging for 24 hours; filtering, washing with distilled water for 5 times to obtain hardwood pulp loaded porous calcium silicate wet pulp for later use; preparing softwood pulp loaded porous calcium silicate wet pulp for later use according to the same conditions;
(3) mixing the softwood pulp and hardwood pulp loaded with the porous calcium silicate prepared in the step (2) according to the mass ratio of 5: 3.0, adding water to prepare slurry with the mass percentage concentration of 1.0%, then adding 38.4mg of polyamine polyamide epichlorohydrin resin (PAE), homogenizing, then making sheets by using a rapid Kaithen (Kaithen) former, and then placing the sheets in a drying box to be dried to obtain heavy metal ion filter paper sheets with the mass of 2.583 g.
The results of testing some performance indexes of the samples obtained in examples 1 to 8 are shown in Table 1, and the numbers of the samples are 1 respectively according to the test of national standard GB/T1914-2007 (chemical analysis filter paper)#、2#、3#、4#、5#、6#、7#And 8#。
TABLE 1 Performance index of the samples
Figure BDA0001516814140000081
The results in Table 1 show that the quantification, the fracture length and the wet bursting strength of the obtained sample all reach the technical indexes of chemical analysis filter paper (qualitative) in the national standard GB/T1914-2007.
Example 9
Preparation of Cu-containing2+、Cd2+、Pb2+、Ni2+、Zn2+2000mL of the heavy metal ion mixed simulation solution, wherein the concentration of each ion is 50 mg/L. Taking 10 sheets of prototype filter paper which is cut into 9cm in diameter, putting the prototype filter paper into a Buchner funnel with the diameter of 9cm, adding water for wetting, and starting a suction filter pump to tightly suck the filter paper. Mixing the prepared mixtureThe heavy metal containing solution was poured into a buchner funnel and naturally filtered, and samples were taken at intervals of 200mL of the filtered filtrate to analyze the concentration of the residual heavy metal ions, and the results were measured 10 times in total, as shown in table 2.
TABLE 2 concentration of heavy metal ions in the filtrate
Figure BDA0001516814140000091
As can be seen from Table 2, 1400mL of the simulated heavy metal ion solution was filtered, and no heavy metal ion was detected in the filtrate; when the solution is filtered to 1600mL, Ni begins to appear in the filtrate2+And Zn2+But at very low concentrations; as the amount of filtration increased, Cu gradually appeared in the filtrate2+And Cd2+When 2000mL of the filtrate is filtered, only Pb is present2+It was not detected. Therefore, the sample can be used as a filter medium for heavy metal ions, and the heavy metal ions in the wastewater can be removed in a simple and convenient manner through filtration under a certain treatment capacity.
Example 10
Taking 1600mL of smelting wastewater of a certain smelting plant, wherein the wastewater pollutant indexes are as follows: pH1.79, turbidity 67.3NTU, Cu2+、Pb2+、Cd2+、Cr3+And As3+The concentrations are shown in Table 2. Taking 10 sheets of prototype filter paper which is cut into 9cm in diameter, putting the prototype filter paper into a Buchner funnel with the diameter of 9cm, adding water for wetting, and starting a suction filter pump to tightly suck the filter paper. And pouring the prepared mixed heavy metal solution into a Buchner funnel for natural filtration, and sampling at intervals of 200mL of filtered filtrate to analyze the concentration and turbidity of residual heavy metal ions. The concentration of heavy metal ions was measured by using an A-Analyst 300 type atomic absorption spectrometer (PE, USA), and the turbidity was measured by using a 2100P portable turbidimeter (HACH, USA) 8 times, and the results are shown in Table 3.
TABLE 3 concentration of heavy metal ions in the filtrate of the filtration treatment of smelting wastewater
Figure BDA0001516814140000092
As can be seen from Table 3, 1000mL of wastewater was filtered and the filtrate was examinedHeavy metal ions can not be generated; when 1200mL of the solution is filtered, a trace amount of Cr is detected3+As filtration proceeds, As also appears in the filtrate3+And Cd2+Filtering the solution; the turbidity of the filtrate was substantially close to 0. Therefore, the product has good treatment effect on actual heavy metal wastewater, can not only filter and remove heavy metal ions, but also remove turbidity-causing substances such as suspended matters and the like in the wastewater, and achieves the aim of removing heavy metals and turbidity in one step.
The above are only preferred embodiments of the present invention, and those skilled in the art can make various modifications and changes to the process conditions for preparation according to the above concept of the present invention, and such modifications and changes are also within the spirit of the present invention.

Claims (10)

1. The heavy metal ion filter paper is characterized by being made of wood pulp fibers with porous calcium silicate loaded on the surface, and having the function of filtering and intercepting heavy metal ions;
the preparation method of the heavy metal ion filter paper is characterized by comprising the following steps:
(1) adding water into wood pulp fibers to prepare a slurry with the mass percentage concentration of 4.5-5.0%, pulping on a pulping machine, controlling the pulping time to be 4.5-5.5 h, wherein the light knife is used for defibering for 1-1.5 h, the middle knife is used for defibering for 2.5-3 h, the heavy knife is used for defibering for 1-1.5 h, and the quality control indexes are as follows: the slurry hanging amount is 8.0-8.5 g, and the beating degree is 85-92 DEG SR;
(2) adding the slurry prepared in the step (1) into a reactor, adding water to dilute the slurry until the mass percentage of the fibers is 0.4-0.5%, fully stirring the slurry for 1-2 hours, then adding calcium salt according to the mass ratio of the calcium salt to the wood pulp fibers of 0.5-2.5: 1, continuously stirring the mixture for 1-1.5 hours after the calcium salt is dissolved, and then adding sodium hydroxide to adjust the pH value of the solution to 9.5-10.5; slowly dropwise adding tetraethoxysilane according to the mass ratio of tetraethoxysilane to calcium salt of 1.0-1.2: 1, continuously stirring and reacting for 2-4 hours after dropwise adding, standing and aging for 12-24 hours, filtering, and washing for 3-5 times by using water;
(3) adding water into the wood pulp loaded with the porous calcium silicate cleaned in the step (2) to prepare slurry with the mass percentage concentration of 1.0-1.5%, then adding a wet strength agent with the mass of 0.3-0.8% of that of the slurry, homogenizing, then making sheets by using a rapid Kaiser former, and drying to obtain heavy metal ion filter paper; or homogenizing, making paper according to conventional paper making process, molding, squeezing, and drying to obtain heavy metal ion filter paper.
2. The preparation method of the heavy metal ion filter paper as claimed in claim 1, which is characterized by comprising the following steps:
(1) adding water into wood pulp fibers to prepare a slurry with the mass percentage concentration of 4.5-5.0%, pulping on a pulping machine, controlling the pulping time to be 4.5-5.5 h, wherein the light knife is used for defibering for 1-1.5 h, the middle knife is used for defibering for 2.5-3 h, the heavy knife is used for defibering for 1-1.5 h, and the quality control indexes are as follows: the slurry hanging amount is 8.0-8.5 g, and the beating degree is 85-92 DEG SR;
(2) adding the slurry prepared in the step (1) into a reactor, adding water to dilute the slurry until the mass percentage of the fibers is 0.4-0.5%, fully stirring the slurry for 1-2 hours, then adding calcium salt according to the mass ratio of the calcium salt to the wood pulp fibers of 0.5-2.5: 1, continuously stirring the mixture for 1-1.5 hours after the calcium salt is dissolved, and then adding sodium hydroxide to adjust the pH value of the solution to 9.5-10.5; slowly dropwise adding tetraethoxysilane according to the mass ratio of tetraethoxysilane to calcium salt of 1.0-1.2: 1, continuously stirring and reacting for 2-4 hours after dropwise adding, standing and aging for 12-24 hours, filtering, and washing for 3-5 times by using water;
(3) adding water into the wood pulp loaded with the porous calcium silicate cleaned in the step (2) to prepare slurry with the mass percentage concentration of 1.0-1.5%, then adding a wet strength agent with the mass of 0.3-0.8% of that of the slurry, homogenizing, then making sheets by using a rapid Kaiser former, and drying to obtain heavy metal ion filter paper; or homogenizing, making paper according to conventional paper making process, molding, squeezing, and drying to obtain heavy metal ion filter paper.
3. The method for preparing heavy metal ion filter paper according to claim 2, wherein in the step (1), the wood pulp is softwood pulp or hardwood pulp.
4. The method for preparing heavy metal ion filter paper according to claim 2, wherein in the step (2), the calcium salt is water-soluble calcium nitrate, calcium nitrate tetrahydrate, calcium chloride or calcium chloride hexahydrate.
5. The method for preparing heavy metal ion filter paper according to claim 2, wherein in the step (2), the sodium hydroxide is sodium hydroxide solid or sodium hydroxide solution.
6. The preparation method of the heavy metal ion filter paper as claimed in claim 2, wherein in the step (2), the tetraethoxysilane is an industrial grade product with the mass fraction of 99.0%.
7. The method for preparing heavy metal ion filter paper according to claim 2, wherein in the step (2), the reactor is provided with a mechanical stirring and a constant pressure dropping funnel.
8. The preparation method of the heavy metal ion filter paper as claimed in claim 2, wherein the wood pulp loaded with the porous calcium silicate is softwood pulp loaded with the porous calcium silicate or/and hardwood pulp loaded with the porous calcium silicate, and when the wood pulp is the softwood pulp loaded with the porous calcium silicate and the hardwood pulp loaded with the porous calcium silicate, the mass ratio of the softwood pulp loaded with the porous calcium silicate to the hardwood pulp loaded with the porous calcium silicate is 5: 2-3.
9. The method for preparing heavy metal ion filter paper according to claim 2, wherein in the step (3), the wet strength agent is polyamine polyamide epichlorohydrin resin, and the mass fraction is 12.5 +/-0.5%.
10. The method for preparing heavy metal ion filter paper according to claim 2, wherein in the step (3), the model of the rapid kaiser former is type HAD-KZCX-159/200 a.
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