CN108118560A - A kind of heavy metal ion filter paper and preparation method thereof - Google Patents
A kind of heavy metal ion filter paper and preparation method thereof Download PDFInfo
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- CN108118560A CN108118560A CN201711386965.9A CN201711386965A CN108118560A CN 108118560 A CN108118560 A CN 108118560A CN 201711386965 A CN201711386965 A CN 201711386965A CN 108118560 A CN108118560 A CN 108118560A
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- heavy metal
- metal ion
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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
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- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to a kind of heavy metal ion filter papers and preparation method thereof.The present invention first by wood pulp cellulose in beater abundant beating, sub-wire, brooming；Then using calcium salt as calcium source, ethyl orthosilicate is silicon source, using wood pulp cellulose as support and reacting environment, teos hydrolysis is made to generate silicate in alkaline conditions and are supported in situ on fiber with calcium binding generation calcium silicates；The softwood pulp of supported porous calcium silicates and hardwood pulp are mixed in a certain ratio again, add in wet strength agent, filter paper is manufactured paper with pulp into after homogenate, not only overcome the shortcomings that synthesis porous calcium silicate is generally needed to be added template or is carried out under Ultrasonic Conditions, it can also make the calcium silicates high degree of dispersion of generation and be firmly bonded on fiber, improve the stability of the supported porous calcium silicates filtrate of cellulose, by manufacturing paper with pulp into filter paper, it is made to possess the ability of absorption retention heavy metal ions in wastewater, realize the heavy metal that can be removed by commonly filtering in waste water, with wide application value.
Description
Technical field
The present invention relates to heavy metal containing wastewater treatment field, more particularly, to a kind of heavy metal ion filter paper and its preparation side
Method.
Background technology
More and more heavy metal ion can be discharged into environment, and has caused serious environmental pollution, has endangered people's body and be good for
Health.Heavy metal pollution has become one of whole world environmental problem the most intractable.To reduce the harm of heavy metal, people have made perhaps
It is make great efforts to eliminate heavy metal more.Absorption method is a kind of one of most common processing method, due to treatment process is simple, operation
It is convenient, treatment effeciency is higher, suitable for low concentration particularly waste water advanced treating and by the favor of field of water treatment.Sorbing material
It is the key that determine adsorption treatment effect.Activated carbon, zeolite and natural clay are since the structure of itself limits, active function groups
It is few, it is typically small to the adsorption capacity of heavy metal.Synthesize sorbing material due to can according to absorption object the characteristics of and adsorption treatment
It is required that be designed, it can generally reach preferable effect, but often there are sorbing material manufacture is more difficult, and cost is higher etc.
Problem.
The separation method for finding, researching and developing fast and convenient heavy metal ion is always what heavy metal containing wastewater treatment field was made great efforts
Direction.Filtering is a kind of most common suspended matter separation method, and separative efficiency is high, and speed is fast, at low cost.But due to heavy metal from
Seed degree is small, hydrated ionic radius generally in below 1nm, using common filtering can not catching heavy metal ion, even if micro-filtration,
Ultrafiltration and nanofiltration also can not catching heavy metal ion, therefore, it is necessary to be improved to filter material (material) or to heavy metal ion form
It is changed, if micelle reinforced hyperfiltration and polymer reinforced ultrafiltration are exactly to wrap up heavy metal ion by adding in surfactant
It is fixed in micella or by polymer heavy metal ion on polymer to increase the granularity of heavy metal ion, so as to ultrafiltration
Film retains.Filter material (material) is improved, is on the one hand to be further reduced filter pore size, is on the other hand by modifying, loading
Active material improves the absorption interception capacity to heavy metal.By these measures, allow separating beavy metal as commonly filtering one
Sample is easy.
The content of the invention
For filter material (material) used in above-mentioned Heavymetal Wastewater Treatment by Adsorption and ordinary filtration there are the problem of, this hair
It is bright that a kind of heavy metal ion filter paper is provided, it manufactures paper with pulp for the wood pulp cellulose of area load porous calcium silicate, there is filtering
The function of catching heavy metal ion, its main feature is that：(1) closed in situ in the presence of the cellulose by mashing height sub-wire, brooming
Paired heavy metal ion has the porous calcium silicate of strong adsorption capacity, and calcium silicates is made to be highly dispersed at by template and support of cellulose
It in fiber, and is rigidly attached on fiber, improves absorption interception capacity and stability to heavy metal；(2) with supported porous silicon
The fiber of sour calcium is raw material, is equipped with the auxiliary materials such as wet strength agent, manufactures paper with pulp into filter paper, is filtered for heavy metal wastewater thereby, can make heavy metal point
Simply facilitate from as common filtering；(3) higher heavy metal interception capacity and excellent waste water permeability are had both, it can be real
It is disposably peace and quiet to reach processing water for the separated in synchronization of suspended matter and water-soluble heavy metal ion in existing waste water.
Another object of the present invention is the preparation method for providing above-mentioned heavy metal ion filter paper, includes the following steps：
(1) water is added to be configured to the slurry that mass percentage concentration is 4.5~5.0% wood pulp cellulose, is carried out on beater
Mashing, beating time control is in 4.5~5.5h, wherein light knife discongests 1.~1.5h, 2.5~3h of middle knife beating, and weight knife beating 1~
1.5h, quality control index：Hanging 8.0~8.5g of amount, beating degree are 85~92 ° of SR；
(2) slurry that step (1) prepares is taken to be added in reactor, is diluted with water to fiber quality percentage as 0.4
~0.5%, 1~2h is sufficiently stirred, then calcium salt is added in for 0.5~2.5: 1 by calcium salt and wood pulp cellulose mass ratio, treats that calcium salt is molten
Continue 1~1.5h of stirring after solution, it is 9.5~10.5 that repeated hydrogenation sodium oxide molybdena, which adjusts pH value of solution,；Then ethyl orthosilicate and calcium salt are pressed
The amount ratio of substance ethyl orthosilicate is slowly added dropwise for 1.0~1.2: 1, continue to be stirred to react 2~4h after dripping off, it is still aging
12~for 24 hours, filtering is washed with water and washs 3~5 times；
(3) wood pulp for the supported porous calcium silicates for cleaning step (2) add water be made into mass percentage concentration for 1.0~
Then 1.5% slurry adds in the wet strength agent of stock quality 0.3~0.8%, after homogenate, be molded with quick kayser (Kaithen)
Device handsheet is drying to obtain heavy metal ion filter paper；Or after homogenate, routinely filter paper papermaking process papermaking, shaping squeezing, drying
Up to heavy metal ion filter paper.
Further, in step (1), wood pulp is softwood pulp or hardwood pulp.
Further, the water of step (1) and (2) is clean tap water.
Further, in step (2), calcium salt is water-soluble calcium nitrate, four water-calcium nitrate, calcium chloride or six water chlorinations
Calcium.
Further, in step (2), sodium hydroxide is sodium hydrate solid or sodium hydroxide solution.
Further, in step (2), ethyl orthosilicate is that mass fraction is 99.0% technical grade product.
Further, in step (2), reactor carries mechanical agitation and constant pressure funnel.
Further, in step (3), the wood pulp of supported porous calcium silicates for supported porous calcium silicates softwood pulp or/
With the hardwood pulp of supported porous calcium silicates, when the softwood pulp for supported porous calcium silicates and the broad-leaved of supported porous calcium silicates
During wood pulp, both front and rear mass ratio is 5: 2~3.
Further, in step (3), wet strength agent is polyamines polyamine epichlorohydrin resin (PAE), and mass fraction is
12.5 ± 0.5%.
Further, in step (3), the model HAD-KZCX-159/200A of quick kayser (Kaithen) former
Type.
The present invention relates to a kind of heavy metal ion filter papers and preparation method thereof.The present invention is first by wood pulp cellulose in beater
In fully beating, sub-wire, brooming；Then using calcium salt as calcium source, ethyl orthosilicate is silicon source, using wood pulp cellulose as support and reaction
Place makes teos hydrolysis generate silicate and is supported on fibre in situ with calcium binding generation calcium silicates in alkaline conditions
On dimension element；The softwood pulp of the supported porous calcium silicates of acquisition and hardwood pulp are mixed in a certain ratio again, add in wet strength agent,
Filter paper is manufactured paper with pulp into after homogenate, not only overcome synthesis porous calcium silicate be generally needed to be added template or under Ultrasonic Conditions into
The shortcomings that row, moreover it is possible to make the calcium silicates high degree of dispersion of generation and be firmly bonded on fiber, it is supported porous to improve cellulose
The stability of calcium silicates filtrate by manufacturing paper with pulp into filter paper, makes it possess the ability of absorption retention heavy metal ions in wastewater, in fact
The purpose of heavy metal in waste water is now removed by commonly filtering.
The present invention is possessed compared with prior art to be had the beneficial effect that：
(1) porous calcium silicate for having strong adsorption capacity to contents of many kinds of heavy metal ion is loaded on cellulose and copied by the present invention
Filter paper is caused, filter paper is assigned to the absorption retention functions of heavy metal ions in wastewater, makes heavy metal containing wastewater treatment as commonly suspending
Object filtration treatment is equally simple and facilitates.Therefore, the present invention has not only developed the processing method of heavy metal wastewater thereby, but also expands
Application method of the porous calcium silicate as efficient heavy wastewater treatment material, makes porous calcium silicate in heavy metal containing wastewater treatment
More practicability.
(2) the method for the present invention is the synthesis of calcium silicates by wood pulp cellulose raw material by being beaten abundant beating, sub-wire and brooming
Abundant place is provided with attachment, and plays the role of template, promotes the generation and growth of calcium silicates.And due to silicon
Sour calcium is generated and grown on the fiber of height sub-wire and brooming, and therefore, not only amalgamation is good for calcium silicates and the fiber of load, and
And stability is also high.
(3) product of the present invention can pass through one step of filter operation as the waste water filtering paper containing all kinds of heavy metal ion
Insoluble suspended matter and soluble heavy metal ion in waste water are removed, achievees the purpose that purification of heavy metal waste water, it therefore, can
Simplify the processing procedure of heavy metal wastewater thereby, there is wide application value and application prospect.
(4) preparation method of the invention, technological process is simple, and operating condition is mild, easily controllable, and need not be special
Or complicated equipment, small investment, easy to popularize and realization industrialization.
Product of the present invention is suitable for the filtration treatment of various heavy metal wastewater therebies.
Description of the drawings
Fig. 1 is the preparation process FB(flow block) of the present invention；
Fig. 2 is the infrared spectrogram of 1 gained hardwood pulp of the embodiment of the present invention and its supported porous calcium silicate material；
Fig. 3 is the scanning electron microscope (SEM) photograph of the supported porous calcium silicate material of 1 softwood pulp of the embodiment of the present invention.
Fig. 4 is the scanning electron microscope (SEM) photograph of the supported porous calcium silicate material of 1 hardwood pulp of the embodiment of the present invention.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1
(1) take softwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 5.0%, on ZDC type beaters
Mashing, light knife discongest 1.0h, middle knife beating 3h, weight knife beating 1.5h, common 5.5h.It is 8.8g to measure hanging amount, and beating degree is 90 °
SR；
Hardwood pulp is beaten by the same terms, it is 9.0g to measure hanging amount, and beating degree is 92 ° of SR；
(2) the softwood pulp wet slurry 100g that step (1) is accomplished fluently is taken to be added in the three-necked bottle of 1500mL, is diluted with water to
Fiber quality percentage is 0.4%, is sufficiently stirred 2h, adds 10.15g four water-calcium nitrates, continue to stir after stirring and dissolving
Then 1.5h adds in solid NaOH and adjusts pH to 10.1；Then slow 10.85g mass fractions are 99.0% ethyl orthosilicate,
The reaction was continued at room temperature after dripping off 4h, it is still aging for 24 hours；Filtering, is washed with distilled water 5 times, it is supported porous to obtain softwood pulp
Calcium silicates wet slurry, it is spare；The supported porous calcium silicates wet slurry of hardwood pulp is prepared by same condition, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 2 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.5%, then adds in 33.6mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.562g.
The sample of hardwood pulp and resulting materials does infrared spectrum analysis in Example 1, and the results are shown in Figure 2；Implement
The scanning electron microscope analysis of softwood pulp and the supported porous calcium silicates of hardwood pulp is distinguished as shown in Figure 3 and Figure 4 in example 1.
Hardwood pulp infrared spectrum characteristic peak can belong to as follows in Fig. 2：3386.9cm-1Absworption peak is-OH bases in cellulose
Stretching vibration absworption peak, 2894.7cm-1The absworption peak at place is attributed to the stretching vibration peak of C-H, 1635.6cm-1Absworption peak
It is attributed to the stretching vibration peak of C=O, 1429.6cm-1The absworption peak at place is-CH2- deformation vibration peak, 1369.7 Hes
1302.4cm-1The absworption peak at place is-CH3With-CH2- flexural vibrations peak, 1168.3 and 1036.6cm-1The absworption peak at place can
It is attributed to the stretching vibration peak of C-O, 784.1cm-1For annular C-O-C asymmetric faces external extension vibration peaks, 6680.5~
543.7cm-1The absworption peak at place is-OH out-of-plane deformation vibration peaks.Compared with hardwood pulp infrared spectrum, supported porous calcium silicates
Afterwards, corresponding absworption peak peak position and peak intensity are changed, also in 1457.3,982.8,933.4,785.7 and 468.5cm-1
Etc. there is new absworption peak, these absworption peaks can belong to as follows：1457.3cm-1For SiO3 2-Characteristic absorption peak,
982.8cm-1For the stretching vibration peak of Si-OH, belong to SiO4Tetrahedral characteristic peak, 933.4cm-1For O-H in Si-OH
Flexural vibrations peak, 785.7 and 468.5cm-1For the stretching vibration peak of Si-O-Si.These results have shown porous calcium silicate
Load is on cellulose.
Fig. 3 and Fig. 4 can be seen that fiber in the supported porous calcium silicates of softwood pulp, and, to be long linear, calcium silicates is adhered to fibre
On the surface of dimension, hardwood pulp fiber is in silk ribbon shape, and calcium silicates is adhered to its surface or the gap of sub-wire intersection.Both tables
Bright, porous calcium silicate has firmly been adhered on fiber.
The characterization result of remaining embodiment resulting materials is basically identical.
Embodiment 2
(1) take hardwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 4.5%, on ZDC type beaters
Mashing, light knife discongest 1.5h, middle knife beating 2.5h, weight knife beating 1h, common 5h.It is 8.5g to measure hanging amount, and beating degree is 89 °
SR；
Softwood pulp is beaten by the same terms, it is 8.3g to measure hanging amount, and beating degree is 87 ° of SR；
(2) take the hardwood pulp wet slurry 112g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel and
In churned mechanically three-necked bottle, it is 0.5% to be diluted with water to fiber quality percentage, is sufficiently stirred 1h, adds 5.10g tetra-
Water calcium nitrate, continues after stirring and dissolving to stir 1h, then adds in solid NaOH and adjusts pH to 9.50；Then slow 4.54 g mass
Fraction is 99.0% ethyl orthosilicate, the reaction was continued at room temperature after dripping off 3h, still aging 12h；Filtering is washed with distillation
It washs 3 times, obtains the supported porous calcium silicates wet slurry of hardwood pulp, it is spare；The supported porous silicon of softwood pulp is prepared by same condition
Sour calcium wet slurry, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 3 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.2%, then adds in 19.2mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.501g.
Embodiment 3
(1) take softwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 4.75%, in ZDC type beaters
Upper mashing, light knife discongest 1.0h, middle knife beating 2.5h, weight knife beating 1.5h, common 5.0h.Hanging amount is measured as 8.8g, beating degree
For 90 ° of SR；
Hardwood pulp is beaten by the same terms, it is 8.9g to measure hanging amount, and beating degree is 89 ° of SR；
(2) take the softwood pulp wet slurry 105.3g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel
In churned mechanically three-necked bottle, it is 0.45% to be diluted with water to fiber quality percentage, is sufficiently stirred 1.5h, adds 7.60
G four water-calcium nitrates, continue after stirring and dissolving to stir 1.5h, then add in solid NaOH and adjust pH to 10.10；Then slowly
7.45g mass fractions are 99.0% ethyl orthosilicate, the reaction was continued at room temperature after dripping off 3.5h, still aging 18h；It crosses
Filter, is washed with distilled water 4 times, obtains the supported porous calcium silicates wet slurry of softwood pulp, spare；Leaf wood is prepared by same condition
Supported porous calcium silicates wet slurry is starched, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 2.5 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.0%, then adds in 48.0mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.575g.
Embodiment 4
(1) take hardwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 5.0%, on ZDC type beaters
Mashing, light knife discongest 1.0h, middle knife beating 2.5h, weight knife beating 1.5h, common 5.0h.It is 8.9g to measure hanging amount, and beating degree is
91°SR；
Softwood pulp is beaten by the same terms, it is 8.7g to measure hanging amount, and beating degree is 88 ° of SR；
(2) take the hardwood pulp wet slurry 100g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel and
In churned mechanically three-necked bottle, it is 0.5% to be diluted with water to fiber quality percentage, is sufficiently stirred 1.25h, adds 7.06 g
Calcium nitrate, continues after stirring and dissolving to stir 1.5h, then adds in solid NaOH and adjusts pH to 10.50；Then slow 9.96 g matter
Measure the ethyl orthosilicate that fraction is 99.0%, the reaction was continued at room temperature after dripping off 2.5h, still aging 20h；Filtering, with distillation
Water washing 5 times obtains the supported porous calcium silicates wet slurry of hardwood pulp, spare；It is more that softwood pulp load is prepared by same condition
Hole calcium silicates wet slurry, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 2 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.5%, then adds in 28.0mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.523g.
Embodiment 5
(1) take hardwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 4.5%, on ZDC type beaters
Mashing, light knife discongest 1.0h, middle knife beating 3.0h, weight knife beating 1.0h, common 5.5h.It is 8.5g to measure hanging amount, and beating degree is
86°SR；
Softwood pulp is beaten by the same terms, it is 8.2g to measure hanging amount, and beating degree is 85 ° of SR；
(2) take the hardwood pulp wet slurry 112g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel and
In churned mechanically three-necked bottle, it is 0.45% to be diluted with water to fiber quality percentage, is sufficiently stirred 1.5h, adds 3.53g
Calcium nitrate, continues after stirring and dissolving to stir 1h, then adds in solid NaOH and adjusts pH to 9.5；Then slow 4.53g mass point
Number is 99.0% ethyl orthosilicate, the reaction was continued at room temperature after dripping off 2h, still aging 12h；Filtering, is washed with distilled water
3 times, the supported porous calcium silicates wet slurry of hardwood pulp is obtained, it is spare；The supported porous silicic acid of softwood pulp is prepared by same condition
Calcium wet slurry, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 2.5 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.3%, then adds in 36.0mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.495g.
Embodiment 6
(1) take softwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 4.5%, on ZDC type beaters
Mashing, light knife discongest 1.0h, middle knife beating 2.5h, weight knife beating 1h, common 4.5h.It is 8.0g to measure hanging amount, and beating degree is 85 °
SR；
Hardwood pulp is beaten by the same terms, it is 8.4g to measure hanging amount, and beating degree is 87 ° of SR；
(2) take the softwood pulp wet slurry 112g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel and
In churned mechanically three-necked bottle, it is 0.45% to be diluted with water to fiber quality percentage, is sufficiently stirred 1h, adds 2.5g chlorine
Change calcium, continue to stir 1.5h after stirring and dissolving, then add in solid NaOH and adjust pH to 9.8；Then slow 5.69g mass point
Number is 99.0% ethyl orthosilicate, the reaction was continued at room temperature after dripping off 3h, still aging 15h；Filtering, is washed with distilled water
4 times, the supported porous calcium silicates wet slurry of softwood pulp is obtained, it is spare；The supported porous silicic acid of hardwood pulp is prepared by same condition
Calcium wet slurry, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 2.8 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.2%, then adds in 43.7mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.538g.
Embodiment 7
(1) take softwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 5.0%, on ZDC type beaters
Mashing, light knife discongest 1.0h, middle knife beating 3h, weight knife beating 1h, common 5h.It is 8.4g to measure hanging amount, and beating degree is 87 ° of SR；
Hardwood pulp is beaten by the same terms, it is 8.7g to measure hanging amount, and beating degree is 88 ° of SR；
(2) take the softwood pulp wet slurry 100g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel and
In churned mechanically three-necked bottle, it is 0.4% to be diluted with water to fiber quality percentage, is sufficiently stirred 1.5h, adds 4.77 g
Calcium chloride, continues after stirring and dissolving to stir 1.5h, then adds in solid NaOH and adjusts pH to 10.2；Then slow 9.04 g mass
Fraction is 99.0% ethyl orthosilicate, the reaction was continued at room temperature after dripping off 4h, it is still aging for 24 hours；Filtering is washed with distillation
It washs 5 times, obtains the supported porous calcium silicates wet slurry of softwood pulp, it is spare；The supported porous silicon of hardwood pulp is prepared by same condition
Sour calcium wet slurry, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 2.2 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.0%, then adds in 34.6mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.521g.
Embodiment 8
(1) take hardwood pulp 150kg that water is added to be configured to the slurry that mass percentage concentration is 5.0%, on ZDC type beaters
Mashing, light knife discongest 1.0h, middle knife beating 3h, weight knife beating 1.5h, common 5.5h.It is 9.0g to measure hanging amount, and beating degree is 91 °
SR；
Softwood pulp is beaten by the same terms, it is 9.0g to measure hanging amount, and beating degree is 88 ° of SR；
(2) take the hardwood pulp wet slurry 100g that step (1) is accomplished fluently be added to 1500mL equipped with constant pressure funnel and
In churned mechanically three-necked bottle, it is 0.5% to be diluted with water to fiber quality percentage, is sufficiently stirred 2h, adds six water of 7.5g
Calcium chloride, continues after stirring and dissolving to stir 1.5h, then adds in solid NaOH and adjusts pH to 9.9；Then slow 7.92 g mass
Fraction is 99.0% ethyl orthosilicate, the reaction was continued at room temperature after dripping off 5h, it is still aging for 24 hours；Filtering is washed with distillation
It washs 5 times, obtains the supported porous calcium silicates wet slurry of hardwood pulp, it is spare；The supported porous silicon of softwood pulp is prepared by same condition
Sour calcium wet slurry, it is spare；
(3) softwood pulp for the supported porous calcium silicates for preparing step (2) and hardwood pulp are mixed for 5: 3.0 in mass ratio
It closes, water is added to be made into the slurry that mass percentage concentration is 1.0%, then adds in 38.4mg polyamines polyamine epichlorohydrin resins
(PAE), after homogenate, with quick kayser (Kaithen) former handsheet, it is subsequently placed in drying box and dries, obtain heavy metal ion
Filter the scraps of paper, quality 2.583g.
The results are shown in Table 1 for the partial properties Indexs measure of 1~embodiment of embodiment, 8 gained sample, by standard GB/T/
T 1914-2007 (chemical analysis filter paper) are examined, and sample number into spectrum is respectively 1#、2#、3#、4#、5#、6#、7#With 8#。
The performance indicator of 1 sample of table
Table 1 the result shows that, the quantitative of obtained sample, fracture length and wet bursting strength have reached standard GB/T/T
The technical indicator of 1914-2007 chemical analyses filter paper (qualitative).
Embodiment 9
It prepares containing Cu2+、Cd2+、Pb2+、Ni2+、Zn2+Heavy metal ion hybrid analog-digital simulation solution 2000mL, wherein each from
Sub- concentration is 50mg/L.The prototype filter paper that 10 handsheets are cut into a diameter of 9cm is taken to be fitted into the Buchner funnel of a diameter of 9cm,
Water is added to soak, starts suction filter pump and filter paper is sucked.The mixture-metal solution of preparation is poured into natural filtration in Buchner funnel, is pressed
Filter liquor is the interval sampling analysis residual heavy metal ion concentration of 200mL, is surveyed 10 times altogether, the results are shown in Table 2.
Concentration of heavy metal ion in 2 filtrate of table
From table 2 it can be seen that filtering the simulation heavy metal ion solution of 1400mL, heavy metal ion is not detected in filtrate；
Start Ni occur when being filled into 1600mL, in filtrate2+And Zn2+, but concentration is very low；As filtration yield increases, progressively go out in filtrate
Existing Cu2+And Cd2+, when filtering 2000mL, only Pb2+It does not detect.As it can be seen that inventive samples can be as the mistake of heavy metal ion
Filter medium under certain treating capacity, can remove the heavy metal ion in waste water by way of filtering this simplicity.
Embodiment 10
The smelting wastewater 1600mL of certain smeltery is taken, Wastewater Pollutant index is as follows：PH1.79, turbidity 67.3NTU, Cu2+、
Pb2+、Cd2+、Cr3+And As3+Concentration is as shown in table 2.The prototype filter paper that 10 handsheets are cut into a diameter of 9cm is taken to be packed into a diameter of 9cm
Buchner funnel in, water is added to soak, start suction filter pump filter paper is sucked.The mixture-metal solution of preparation is poured into Buchner funnel
Middle natural filtration, by the interval sampling analysis residual heavy metal ion concentration and turbidity that filter liquor is 200mL.Heavy metal ion
Concentration is measured using 300 type Atomic Absorption Spectrometers of A-Analyst (PE companies of the U.S.), and turbidity uses the portable turbidity of 2100P
It counts (HACH companies of the U.S.) to measure, survey 8 times altogether, the results are shown in Table 3.
Concentration of heavy metal ion in 3 smelting wastewater filtration treatment filtrate of table
From table 3 it can be seen that filtering 1000mL waste water, heavy metal ion is can't check in filtrate；When filtering 1200mL, just examine
Go out micro Cr3+, as filtering carries out, also there is As in filtrate3+And Cd2+Filtrate；The turbidity of filtrate is substantially near 0.It can
See, product of the present invention has good treatment effect to actual heavy metal wastewater thereby, can not only be filtered to remove heavy metal ion, moreover it is possible to
Absurd creature matter is caused to remove together wherein suspended matter etc., achieve the purpose that a step removes removing heavy metals and turbidity.
The foregoing is merely the preferred embodiments of the present invention, and according to the above-mentioned design, those skilled in the art are also
Can to the process conditions of preparation, various modification can be adapted and conversion, these similar conversion and modification belong to the reality of the present invention
Matter.
Claims (10)
1. a kind of heavy metal ion filter paper, which is characterized in that its for area load porous calcium silicate wood pulp cellulose manufacture paper with pulp and
Into, have the function of filter catching heavy metal ion.
2. the preparation method of a kind of heavy metal ion filter paper described in claim 1, which is characterized in that comprise the following steps：
(1) water is added to be configured to the slurry that mass percentage concentration is 4.5~5.0% wood pulp cellulose, is beaten on beater,
Beating time is controlled in 4.5~5.5h, wherein light knife discongests 1~1.5h, 2.5~3h of middle knife beating, weight knife 1~1.5h of beating,
Quality control index：Hanging 8.0~8.5g of amount, beating degree are 85~92 ° of SR；
(2) slurry that step (1) prepares is taken to be added in reactor, be diluted with water to fiber quality percentage for 0.4~
0.5%, 1~2h is sufficiently stirred, then adds in calcium salt by calcium salt and wood pulp cellulose mass ratio for 0.5~2.5: 1, treats that calcium salt dissolves
After continue 1~1.5h of stirring, it is 9.5~10.5 that repeated hydrogenation sodium oxide molybdena, which adjusts pH value of solution,；Then by ethyl orthosilicate and calcium salt
Ethyl orthosilicate is slowly added dropwise for 1.0~1.2: 1 in the amount ratio of substance, continues to be stirred to react 2~4h after dripping off, still aging 12~
For 24 hours, filter, be washed with water and wash 3~5 times；
(3) it is 1.0~1.5% that the wood pulp for the supported porous calcium silicates for cleaning step (2), which adds water to be made into mass percentage concentration,
Then slurry adds in the wet strength agent of stock quality 0.3~0.8%, after homogenate, with quick kayser former handsheet, is drying to obtain
Heavy metal ion filter paper；Or after homogenate, routinely filter paper papermaking process papermaking, shaping squeezing is drying to obtain heavy metal ion
Filter paper.
3. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that in step (1), wood pulp
For softwood pulp or hardwood pulp.
4. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that in step (2), calcium salt
For water-soluble calcium nitrate, four water-calcium nitrate, calcium chloride or calcium chloride hexahydrate.
5. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that in step (2), hydrogen-oxygen
It is sodium hydrate solid or sodium hydroxide solution to change sodium.
6. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that in step (2), positive silicon
Acetoacetic ester is that mass fraction is 99.0% technical grade product.
7. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that in step (2), reaction
Device carries mechanical agitation and constant pressure funnel.
8. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that supported porous calcium silicates
Wood pulp be the softwood pulp of supported porous calcium silicates or/and the hardwood pulp of supported porous calcium silicates, when for supported porous silicon
During the hardwood pulp of the softwood pulp of sour calcium and supported porous calcium silicates, both front and rear mass ratio is 5: 2~3.
9. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that wet strong in step (3)
Agent is polyamines polyamine epichlorohydrin resin, and mass fraction is 12.5 ± 0.5%.
10. the preparation method of heavy metal ion filter paper according to claim 2, which is characterized in that in step (3), soon
The model HAD-KZCX-159/200A types of fast kayser former.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108999032A (en) * | 2018-09-07 | 2018-12-14 | 宿州学院 | A kind of preparation method of modified plant fibers filter paper |
| CN111379181A (en) * | 2020-03-09 | 2020-07-07 | 内蒙古农业大学 | Method for dissolving, recycling and reusing based on damaged impregnated paper and cut leftover materials of impregnated paper |
| CN115075055A (en) * | 2022-06-15 | 2022-09-20 | 石家庄铁道大学 | Nano magnetic oxide composite tea paper and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608104A (en) * | 2011-02-03 | 2014-02-26 | 萨里大学 | Composite adsorbent material containing a porous carbon matrix |
| CN104016434A (en) * | 2013-03-01 | 2014-09-03 | 北京航空航天大学 | Method for purifying sewage containing heavy metal by utilizing calcium metasilicate and recycling heavy metal |
| CN104878649A (en) * | 2015-05-08 | 2015-09-02 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Preparation method of in-situ calcium silicate fiber pulp and calcium silicate high-filler pulp |
| CN105251438A (en) * | 2015-07-27 | 2016-01-20 | 王勇梅 | Fly ash-based adsorption material utilizing fiber as pore forming agent |
-
2017
- 2017-12-20 CN CN201711386965.9A patent/CN108118560B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608104A (en) * | 2011-02-03 | 2014-02-26 | 萨里大学 | Composite adsorbent material containing a porous carbon matrix |
| CN104016434A (en) * | 2013-03-01 | 2014-09-03 | 北京航空航天大学 | Method for purifying sewage containing heavy metal by utilizing calcium metasilicate and recycling heavy metal |
| CN104878649A (en) * | 2015-05-08 | 2015-09-02 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Preparation method of in-situ calcium silicate fiber pulp and calcium silicate high-filler pulp |
| CN105251438A (en) * | 2015-07-27 | 2016-01-20 | 王勇梅 | Fly ash-based adsorption material utilizing fiber as pore forming agent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108999032A (en) * | 2018-09-07 | 2018-12-14 | 宿州学院 | A kind of preparation method of modified plant fibers filter paper |
| CN111379181A (en) * | 2020-03-09 | 2020-07-07 | 内蒙古农业大学 | Method for dissolving, recycling and reusing based on damaged impregnated paper and cut leftover materials of impregnated paper |
| CN111379181B (en) * | 2020-03-09 | 2021-09-14 | 内蒙古农业大学 | Method for dissolving, recycling and reusing based on damaged impregnated paper and cut leftover materials of impregnated paper |
| CN115075055A (en) * | 2022-06-15 | 2022-09-20 | 石家庄铁道大学 | Nano magnetic oxide composite tea paper and preparation method thereof |
| CN115075055B (en) * | 2022-06-15 | 2023-04-18 | 石家庄铁道大学 | Nano magnetic oxide composite tea paper and preparation method thereof |
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