CN110479307A - A kind of efficiently durable wood-based composite material and preparation method except formaldehyde - Google Patents

A kind of efficiently durable wood-based composite material and preparation method except formaldehyde Download PDF

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Publication number
CN110479307A
CN110479307A CN201910904635.7A CN201910904635A CN110479307A CN 110479307 A CN110479307 A CN 110479307A CN 201910904635 A CN201910904635 A CN 201910904635A CN 110479307 A CN110479307 A CN 110479307A
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China
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solution
timber
preparation
based composites
except formaldehyde
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Inventor
孙庆丰
蔡泰龙
黄琼涛
王喆
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Yihua Life Polytron Technologies Inc
Zhejiang A&F University ZAFU
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Yihua Life Polytron Technologies Inc
Zhejiang A&F University ZAFU
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Priority to CN201910904635.7A priority Critical patent/CN110479307A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention belongs to technical field of composite materials, provide a kind of preparation method of efficiently durable timber based composites except formaldehyde, comprising the following steps: timber is immersed in the mixed solution of nickel salt and ferrous salt, addition urea；It adjusts solution concentration pH value and is adjusted to alkalinity, sealed reaction vessel carries out hydro-thermal reaction, is cooled to room temperature；Chlorine noble metal acid solution is added into solution, adds reducing agent, carries out reduction reaction under room temperature；Timber is taken out, is drying to obtain.The present invention is reacted using low-temperature hydrothermal constructs catalyst activity layer in wood surface, and its catalytic activity is enhanced by decorating noble metal nano particles, make timber while keeping original physicochemical properties, make full use of its natural hierarchical structure and duct absorbing formaldehyde gas abundant, and formaldehyde molecule is captured to improve the catalytic activity of catalyst by the hydroxyl of wood surface, formaldehyde gas is collected into the catalyst oxidation loaded in channel and on timber, resolves into carbon dioxide and water.

Description

A kind of efficiently durable wood-based composite material and preparation method except formaldehyde
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of efficiently durable timber based composites except formaldehyde And preparation method thereof.
Background technique
Timber is a kind of reproducible biological material of green, currently, it is widely used in the side of human lives Aspect face, such as construction and decoration, interior/exterior decoration, Furniture manufacture, packaging material.However, most of wood currently on the market Material product, such as wooden furniture, glued board, Scrimber, wood plastic composite all contain adhesive, resin or glue, to continue Ground release formaldehyde gas causes people by the body harm of many substances, such as the stimulation of eye nose, asthma, headache, chronic branch gas Guan Yan, even cancer.In addition, also to can result in room air long-term for such as common common consumer product of wallpaper, curtain, carpet By formaldehyde pollution.
The method of traditional removal formaldehyde is mainly decorated various porous materials in wood surface and is dropped by physical absorption Content of formaldehyde in the gas of low latitude plays certain air purification effect.But timber original is not only masked using physisorphtion Some colors, decorative pattern, and when the adsorbance of formaldehyde reaches saturation point, suction-operated is no longer obvious, or even it is also possible to release Formaldehyde continues to be detrimental to health out.
In recent years, with the development of nano science, advanced catalysis material progress functionality is constructed in wood surface and is changed It is good also to have become a hot topic of research, such as TiO2、ZnO、SnO2、ZrO2、CeO2Equal inorganic nano materials are passing through all kinds of metallics There is excellent photocatalytic activity after such as Fe, Cu, Ag, Pt, Au improvement, but construct Fe-TiO in wood surface2Etc. advanced After catalysis material, it is also necessary to which other equipment or light source provide energy and carry out catalysis reaction, it is possible to produce unfavorable is secondary Pollutant, and the problems such as optical attenuation can be caused with the activity of the progress catalyst of reaction, thus cannot be clear long-term effectively Except the formaldehyde in room air.
Based on the protection grain of wood, energy saving and permanently effective consideration, preparation should be sought and remain with timber natural goods Physicochemical property, and being capable of energy conservation, new method that is efficient, enduringly removing formaldehyde timber.
Summary of the invention
For the defects in the prior art, the present invention provide a kind of efficiently durable timber based composites except formaldehyde and its Preparation method, to solve the problem of that existing woodwork furniture and ornament materials sustained release formaldehyde are detrimental to health.
In a first aspect, the preparation method of the efficiently durable timber based composites except formaldehyde provided by the invention, including with Lower step:
Step S1: timber is immersed in the mixed solution of nickel salt and ferrous salt, and urea is added thereto；
Step S2: being adjusted to alkalinity using the solution concentration pH value that weak acid strong alkali salt sodium citrate adjusts the step S1, close It seals reaction vessel and carries out hydro-thermal reaction, be cooled to room temperature later；
Chlorine noble metal acid solution is added in the solution of S3: Xiang Suoshu step S2 of step, adds reducing agent, is carried out under room temperature Reduction reaction, reaction equation are as follows:
NaBH4+2H2PtCl6+12NaOH→2Pt+12NaCl+NaB(OH)4+8H2O；
Step S4: taking out the timber in the step S3, it is dry to get.
Optionally, timber used in the step S1 is poplar material, birch material, China fir material or cork wood material；
Need before the timber use to carry out its surface cleaning or polishing treatment, polishing can allow wood surface more It is smooth, facilitate the smooth attachment of catalyst, preventing from reuniting wastes, and selection sand paper polishes manually or machine polishing, at one In preferred embodiment, 1000 mesh, 1200 mesh are successively used, 1500 mesh sand paper are polished；Cleaning is successively to soak in clear water and acetone It carries out being ultrasonically treated each 25 minutes under bubble.
Optionally, in the step S1, the nickel salt is nickel sulfate, nickel chloride or nickel nitrate, and the ferrous salt is sulfuric acid Ferrous, frerrous chloride or ferrous nitrate；
Under normal circumstances, nickel salt and the corresponding cation of ferrous salt should be consistent.
The mixed solution is 2:1 by volume ratio and concentration is the nickel salt solution and ferrous salt solution of 0.01~5mol/L It mixes.
Optionally, it is 0.15~0.20mol/L that the step S1, which is formed by the concentration of urea in solution,.
Optionally, in the step S2, the pH value is 7~9；
The temperature of the hydro-thermal reaction is 60~200 DEG C, and the time is 8~16h.
Optionally, in the step S3, the chlorine noble metal acid is chloroplatinic acid, gold chloride or chlorine palladium acid；
The concentration of the chlorine noble metal acid solution is 0.01~0.1mol/L；
The volume ratio of the chlorine noble metal acid solution and the ferronickel mixed solution being mixed with after urea is 1:99.
Optionally, in the step S3, the reducing agent is the sodium borohydride solution that concentration is 0.1mol/L, and the boron The volume ratio of sodium hydride solution and the chlorine noble metal acid solution is 20:1.
Optionally, in the step S3, the time of the reduction reaction is 1~3h；Wood surface in-situ reducing makes timber There is metallic luster on surface, while generation metal precipitates can be also restored in solution.
Optionally, in the step S4, dry temperature is 40~60 DEG C, and the time is 10~15h.
Second aspect, the present invention provide the preparation method institute of the efficiently durable timber based composites except formaldehyde as mentioned The efficient durable timber based composites except formaldehyde of preparation.
Beneficial effects of the present invention:
1. the preparation method of the efficient durable timber based composites except formaldehyde of the invention, is existed using low-temperature hydrothermal reaction Wood surface constructs catalyst activity layer, and enhances its catalytic activity by decorating noble metal nano particles, and timber is made to exist While keeping original physicochemical properties, its natural hierarchical structure and duct absorbing formaldehyde gas abundant are made full use of, And formaldehyde molecule is captured to improve the catalytic activity of catalyst by the hydroxyl of wood surface, formaldehyde gas is collected into channel And the catalyst oxidation loaded on timber, resolve into carbon dioxide and water.
2. the preparation method of the efficient durable timber based composites except formaldehyde of the invention, simple process, raw material sources Extensively, low in cost, low energy consumption, is suitble to industrialized production.
3. the efficient durable timber based composites except formaldehyde prepared by the present invention, using timber as catalyst activity layer Substrate, not only can be absorbed the formaldehyde in room air, and first can be aoxidized using the LDH catalyst on its surface Aldehyde makes it be decomposed into clean gas, achievees the purpose that really to remove formaldehyde.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art are briefly described.In all the appended drawings, similar element Or part is generally identified by similar appended drawing reference.In attached drawing, each element or part might not be drawn according to actual ratio.
Fig. 1 is the macrograph of the efficient durable timber based composites except formaldehyde prepared by the present invention；
Fig. 2 is 100 times of scanning electron microscope (SEM) photographs of timber based composites shown in Fig. 1；
Fig. 3 is 5000 times of scanning electron microscope (SEM) photographs of timber based composites shown in Fig. 1；
Fig. 4 is the schematic illustration that timber based composites shown in Fig. 1 absorbs formaldehyde and decomposing formaldehyde；
Fig. 5 is formaldehyde time history plot in the embodiment of the present invention 6；
Fig. 6 is carbon dioxide time history plot in the embodiment of the present invention 6.
Specific embodiment
It is described in detail below in conjunction with embodiment of the attached drawing to technical solution of the present invention.Following embodiment is only used for Clearly illustrate technical solution of the present invention, therefore be intended only as example, and cannot be used as a limitation and limit protection of the invention Range.
It should be noted that unless otherwise indicated, technical term or scientific term used in this application should be this hair The ordinary meaning that bright one of ordinary skill in the art are understood.
Using 20mm × 20mm × 1mm wood chip as objective for implementation, its appearance line of different types of timber in the application Reason, density, moisture content, mechanical property etc. are different depending on the application to be reasonably selected, it is however generally that, density is few compared with impurity such as small, resins Timber be easier to be impregnated with modification, the timber more than impurity big for hardness can usually be softened with boiling, with ethyl alcohol acetone etc. remove Impurity not soluble in water.Poplar material, birch material, China fir material and cork wood material, matter are selected in the embodiment of the present application 1- embodiment 5 Ground is soft, easy processing, and more common in the market.
The plain original physicochemical properties of timber generally refer to, and under the conditions of low temperature (≤200 DEG C), timber main component is not sent out Biochemical variation may have part hemicellulose to decompose but influence less, and wet timber mechanical property after drying is complete changes not Greatly.
Fig. 1 is the macrograph of the efficient durable timber based composites except formaldehyde prepared by the present invention；Fig. 2 is Fig. 1 100 times of scanning electron microscope (SEM) photographs of shown timber based composites；Fig. 3 is 5000 times of scannings electricity of timber based composites shown in Fig. 1 Mirror figure.In conjunction with Fig. 1-Fig. 3, the first radial longitudinal section and wall loading in the cell in timber of timber based composites prepared by the present invention NiFe-LDH, i.e. layered double hydroxide, PARA FORMALDEHYDE PRILLS(91,95) have suction-operated；But NiFe-LDH is after temperature and humidity variation Formaldehyde gas is easy to run out of, to be unable to continuous and effective formaldehyde adsorption, therefore, the present invention carried noble metal on NiFe-LDH again Nanoparticle, for keeping the catalytic activity of NiFe-LDH.Fig. 4 is that timber based composites shown in Fig. 1 absorbs formaldehyde and decomposes The schematic illustration of formaldehyde.Referring to fig. 4, in entire catalyst system, Pt/NiFe-LDH plays a major role.Firstly, HCHO molecule It is captured on the surface NiFe-LDH by OH group by hydrogen bond；Next, the table positioned at NiFe-LDH activated by Pt nanoparticle Face O atom attacks the C atom of HCHO, converts dimethoxy for HCHO, dimethoxy will be further converted to formiate object Matter；On the other hand, O2Two active O atoms are generated by the division of Pt nanoparticle, one of them is produced in conjunction with formiate substance Raw carbonic acid, carbonic acid resolve into rapidly CO2And H2O, and Lacking oxygen is left for another active O atom.Therefore, entire Pt/NiFe- LDH system can be restored to its reset condition and start the Degradation Formaldehyde of a new round.
And compared with single NiFe-LDH or Pt/NiFe-LDH powder, the catalyst loaded on timber obviously has Preferably dispersibility, thus there is bigger active region, to obtain superior catalytic activity.Simultaneously by Pt/NiFe- LDH is supported on timber the raw material and process costs that can save LDH and Pt noble metal, can save relative to other loaded articles Such as the cost of material of graphene oxide, and it may be directly applied to construction and decoration.In addition, the wood surface of polyhydroxy can be with Active site is provided for HCHO, to collect formaldehyde gas for LDH catalysis.Columnar cell's chamber of timber serves as conveying formaldehyde gas The channel of body molecule, toxic HCHO gas is collected into channel and the LDH catalyst loaded by cell wall aoxidizes, so Discharge contains CO afterwards2And H2The clean gas of O.
Embodiment 1
The present embodiment provides a kind of preparation methods of efficiently durable timber based composites except formaldehyde, and specific steps are such as Under:
S1: preferred dimension is 20mm × 20mm × 1mm poplar material, carries out cleaning treatment to its surface, is dipped in In the mixed solution of nickel sulfate and ferrous sulfate, wherein the concentration of nickel sulfate solution and ferrous sulfate solution is 0.08mol/ L, nickel sulfate solution volume are 100ml, and ferrous sulfate solution volume is 50ml, then urea is added thereto reaches its concentration 0.16mol/L；
S2: 8 are adjusted to using the solution concentration pH value that sodium citrate adjusts S1, sealed reaction vessel is lauched in 100 DEG C of conditions Thermal response 13h, is cooled to room temperature later；
S3: the platinum acid chloride solution that concentration is 0.1mol/L is added into the solution of S2, wherein platinum acid chloride solution and ferronickel are mixed The volume ratio for closing solution is 1:99, adds the sodium borohydride solution that concentration is 0.1mol/L, reduction reaction 3h under room temperature, In, the volume ratio of sodium borohydride solution and platinum acid chloride solution is 20:1；
S4: taking out the timber in S3, under the conditions of 40 DEG C dry 15h to get.
Embodiment 2
The present embodiment provides a kind of preparation methods of efficiently durable timber based composites except formaldehyde, and specific steps are such as Under:
S1: preferred dimension is 20mm × 20mm × 1mm birch material, is processed by shot blasting, is dipped in its surface In the mixed solution of nickel chloride and frerrous chloride, wherein the concentration of nickel chloride solution and solution of ferrous chloride is 2mol/L, chlorine Change nickel solution volume is 100ml, and solution of ferrous chloride volume is 50ml, then urea is added thereto reaches its concentration 0.20mol/L；
S2: 8 are adjusted to using the solution concentration pH value that sodium citrate adjusts S1, sealed reaction vessel is lauched in 180 DEG C of conditions Thermal response 11h, is cooled to room temperature later；
S3: the chlorauric acid solution that concentration is 0.01mol/L is added into the solution of S2, wherein chlorauric acid solution and ferronickel The volume ratio of mixed solution is 1:99, adds the sodium borohydride solution that concentration is 0.1mol/L, reduction reaction 1h under room temperature, In, the volume ratio of sodium borohydride solution and chlorauric acid solution is 20:1；
S4: taking out the timber in S3, under the conditions of 50 DEG C dry 12h to get.
Embodiment 3
The present embodiment provides a kind of preparation methods of efficiently durable timber based composites except formaldehyde, and specific steps are such as Under:
S1: preferred dimension is 20mm × 20mm × 1mm China fir material, is processed by shot blasting, is dipped in its surface In the mixed solution of nickel nitrate and ferrous nitrate, wherein the concentration of nickel nitrate solution and ferrous nitrate solution is 0.01mol/ L, nickel nitrate solution volume are 100ml, and ferrous nitrate solution volume is 50ml, then urea is added thereto reaches its concentration 0.15mol/L；
S2: 8 are adjusted to using the solution concentration pH value that sodium citrate adjusts S1, sealed reaction vessel is lauched in 60 DEG C of conditions Thermal response 16h, is cooled to room temperature later；
S3: the chlorine palladium acid solution that concentration is 0.06mol/L is added into the solution of S2, wherein chlorine palladium acid solution and ferronickel The volume ratio of mixed solution is 1:99, adds the sodium borohydride solution that concentration is 0.1mol/L, reduction reaction 2h under room temperature, In, the volume ratio of sodium borohydride solution and chlorine palladium acid solution is 20:1；
S4: taking out the timber in S3, under the conditions of 60 DEG C dry 10h to get.
Embodiment 4
The present embodiment provides a kind of preparation methods of efficiently durable timber based composites except formaldehyde, and specific steps are such as Under:
S1: preferred dimension is 20mm × 20mm × 1mm cork wood material, carries out cleaning treatment to its surface, is dipped in In the mixed solution of nickel sulfate and ferrous sulfate, wherein the concentration of nickel sulfate solution and ferrous sulfate solution is 5mol/L, sulphur Sour nickel solution volume is 100ml, and ferrous sulfate solution volume is 50ml, then urea is added thereto reaches its concentration 0.20mol/L；
S2: 7 are adjusted to using the solution concentration pH value that sodium citrate adjusts S1, sealed reaction vessel is lauched in 200 DEG C of conditions Thermal response 8h, is cooled to room temperature later；
S3: the chlorauric acid solution that concentration is 0.08mol/L is added into the solution of S2, wherein chlorauric acid solution and ferronickel The volume ratio of mixed solution is 1:99, adds the sodium borohydride solution that concentration is 0.1mol/L, reduction reaction 2h under room temperature, In, the volume ratio of sodium borohydride solution and chlorauric acid solution is 20:1；
S4: taking out the timber in S3, under the conditions of 50 DEG C dry 11h to get.
Embodiment 5
The present embodiment provides a kind of preparation methods of efficiently durable timber based composites except formaldehyde, and specific steps are such as Under:
S1: preferred dimension is 20mm × 20mm × 1mm poplar material, is processed by shot blasting, is dipped in its surface In the mixed solution of nickel sulfate and ferrous sulfate, wherein the concentration of nickel sulfate solution and ferrous sulfate solution is 1mol/L, sulphur Sour nickel solution volume is 100ml, and ferrous sulfate solution volume is 50ml, then urea is added thereto reaches its concentration 0.15mol/L；
S2: 9 are adjusted to using the solution concentration pH value that sodium citrate adjusts S1, sealed reaction vessel is lauched in 150 DEG C of conditions Thermal response 12h, is cooled to room temperature later；
S3: the platinum acid chloride solution that concentration is 0.05mol/L is added into the solution of S2, wherein platinum acid chloride solution and ferronickel The volume ratio of mixed solution is 1:99, adds the sodium borohydride solution that concentration is 0.1mol/L, reduction reaction 2h under room temperature, In, the volume ratio of sodium borohydride solution and platinum acid chloride solution is 20:1；
S4: taking out the timber in S3, under the conditions of 50 DEG C dry 13h to get.
Comparative example 1
This comparative example provides one kindFerronickel LDH is loaded on timberTimber based composites preparation method, it is specific to walk It is rapid as follows:
S1: preferred dimension is 20mm × 20mm × 1mm poplar material, carries out cleaning treatment to its surface, is dipped in In the mixed solution of nickel sulfate and ferrous sulfate, wherein the concentration of nickel sulfate solution and ferrous sulfate solution is 0.08mol/ L, nickel sulfate solution volume are 100ml, and ferrous sulfate solution volume is 50ml, then urea is added thereto reaches its concentration 0.16mol/L；
S2: 8 are adjusted to using the solution concentration pH value that sodium citrate adjusts S1, sealed reaction vessel is lauched in 100 DEG C of conditions Thermal response 13h, is cooled to room temperature later；
S3: taking out the timber in S2, under the conditions of 40 DEG C dry 15h to get.
Comparative example 2
This comparative example provides one kindThe carried noble metal nano platinum particle on timberPreparation method, the specific steps are as follows:
S1: preferred dimension is 20mm × 20mm × 1mm poplar material, carries out cleaning treatment to its surface, is dipped in dense Degree is to add the sodium borohydride solution that concentration is 0.1mol/L, reduction reaction under room temperature in the platinum acid chloride solution of 0.1mol/L 3h, wherein the volume ratio of sodium borohydride solution and platinum acid chloride solution is 20:1；
S2: taking out the timber in S1, under the conditions of 40 DEG C dry 15h to get.
Embodiment 6:
By sample prepared by embodiment 1, comparative example 1, comparative example 2 and do not occur any reaction plain timber (having a size of 20mm × 20mm × 1mm poplar material) it is sealed in glass culture dish as objective for implementation；
Firstly, preparing a volume is 0.01m3Shading closed container as reaction vessel, reaction vessel interior also It is mounted with that a small fan keeps internal gas flow；Then, the sample being sealed in glass culture dish is put into reaction vessel In；Then, by mass concentration be 38% formalin outside reaction vessel 45 DEG C of heating generate formaldehyde gas and be passed through instead It answers in container, until the concentration of formaldehyde in reaction vessel reaches stable 0.2mgm-3.Opening glass culture dish reacts catalysis It carries out.The formaldehyde and CO of different time2Concentration is detected by air mass monitor.
Fig. 5 is formaldehyde time history plot in the embodiment of the present invention 6.As seen from Figure 5, it is made in embodiment 1 The effect of standby sample removal formaldehyde is best.
Fig. 6 is carbon dioxide time history plot in the embodiment of the present invention 6.As seen from Figure 6, embodiment 1 The corresponding gas concentration lwevel of the sample of middle preparation persistently rises, illustrate the sample prepared in embodiment 1 lasting absorption simultaneously Decomposing formaldehyde.
Unless specifically stated otherwise, the numerical value otherwise illustrated in these embodiments is not limit the scope of the invention.In In all examples shown and described herein, unless otherwise prescribed, any occurrence should be construed as merely illustratively, and Not by way of limitation, therefore, other examples of exemplary embodiment can have different values.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme should all cover within the scope of the claims and the description of the invention.

Claims (10)

1. a kind of preparation method of the efficiently durable timber based composites except formaldehyde, which comprises the following steps:
Step S1: timber is immersed in the mixed solution of nickel salt and ferrous salt, and urea is added thereto；
Step S2: the solution concentration pH value for adjusting the step S1 is adjusted to alkalinity, and sealed reaction vessel carries out hydro-thermal reaction, later It is cooled to room temperature；
Chlorine noble metal acid solution is added in the solution of S3: Xiang Suoshu step S2 of step, adds reducing agent, is restored under room temperature Reaction；
Step S4: taking out the timber in the step S3, it is dry to get.
2. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that Timber used in the step S1 is poplar material, birch material, China fir material or cork wood material；
It needs to carry out its surface cleaning or polishing treatment before the timber use.
3. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that In the step S1, the nickel salt be nickel sulfate, nickel chloride or nickel nitrate, the ferrous salt be ferrous sulfate, frerrous chloride or Ferrous nitrate；
The mixed solution is 2:1 by volume ratio and concentration is that the nickel salt solution of 0.01~5mol/L and ferrous salt solution mix It forms.
4. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that The concentration that the step S1 is formed by urea in solution is 0.15~0.20mol/L.
5. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that In the step S2, the pH value is 7~9；
The temperature of the hydro-thermal reaction is 60~200 DEG C, and the time is 8~16h.
6. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that In the step S3, the chlorine noble metal acid is chloroplatinic acid, gold chloride or chlorine palladium acid；
The concentration of the chlorine noble metal acid solution is 0.01~0.1mol/L；
The volume ratio of the chlorine noble metal acid solution and the ferronickel mixed solution is 1:99.
7. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that In the step S3, the reducing agent is the sodium borohydride solution that concentration is 0.1mol/L, and the sodium borohydride solution and institute The volume ratio for stating chlorine noble metal acid solution is 20:1.
8. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that In the step S3, the time of the reduction reaction is 1~3h.
9. the preparation method of the efficiently durable timber based composites except formaldehyde according to claim 1, which is characterized in that In the step S4, dry temperature is 40~60 DEG C, and the time is 10~15h.
10. such as the preparation method institute of the efficiently durable timber based composites except formaldehyde according to any one of claims 1 to 9 The efficient durable timber based composites except formaldehyde of preparation.
CN201910904635.7A 2019-09-24 2019-09-24 A kind of efficiently durable wood-based composite material and preparation method except formaldehyde Pending CN110479307A (en)

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Application publication date: 20191122