CN104368325A - Preparation method of formaldehyde-photodegrading honeycomb activated carbon - Google Patents

Abstract

Disclosed is a preparation method of formaldehyde-photodegrading honeycomb activated carbon. The method is characterized by including: putting powdered activated carbon in a home-made cellophane mould, adding a black material prior to mixing for a certain period of time, rapidly adding a white material, performing high-speed mixing prior to free foaming, carrying out room-temperature curing prior to forming, putting the formed material in a muffle furnace for high-temperature heat treatment prior to obtaining the honeycomb activated carbon, subjecting TiO2 nano particles of P-25 type to ultrasonic dispersion to form suspension liquid, completely immersing the prepared honeycomb activated carbon into the suspension liquid, and performing heat treatment to prepare a P-25/activated carbon composite having good photocatalytic degradation performance on indoor formaldehyde. The operation process has the main advantages that that the operation method is simple, the prepared honeycomb activated carbon is large in specific surface area and high in adsorptive property, can be prepared into arbitrary shape, has good catalytic degradation performance on indoor formaldehyde gas and is reusable, low in production cost and applicable to removal of formaldehyde gas after home decoration, and after the honeycomb activated carbon is loaded with P-25, the P-25 nano particles are evenly dispersed in the surface and pores of the honeycomb activated carbon.

Description

A kind of preparation method of light degradation formaldehyde cellular activated carbon

Art:

The present invention relates to field of inorganic nano-material preparation, particularly relate to a kind of preparation method of light degradation formaldehyde cellular activated carbon.

Background technology:

Room air pollution becomes one of harm humans healthy most important " stealthy killer " gradually, more than 500 kind of volatile organic matter is there is in room air, wherein formaldehyde, benzene homologues etc. mainly contain poisonous gas, 2004 IARC (IARC) on No. 153 " formaldehyde is carcinogenic " publications, formaldehyde is defined as carcinogenic substance, it is mainly derived from finishing material, furniture, coating, wood-based plate and the adhesive etc. that relate in decorations.National Standard of the People's Republic of China's sanitary standard of formaldehyde " in indoor air " regulation, in indoor air, formaldehyde maximum permissible concentration is 0.08mg/m ³, the content of formaldehyde usually between finishing back room is all more than more than 10 times, and the time limit of hiding reaches 10 ~ 15 years, therefore seeks effective way removal indoor formaldehyde and has far-reaching practical significance.

The method of now widely used removal indoor formaldehyde mainly comprises absorption method, oxidation degradation method, photocatalyst edman degradation Edman etc.Wherein the adsorbent saturated extent of adsorption of absorption method is difficult to control, and adsorbent easy in inactivation cannot be used widely; Oxidation degradation method is carried noble metal or metallorganic on all kinds of porous carbon material generally, utilize the oxygen in air, Degradation Formaldehyde is become the Small molecular such as carbon dioxide and water, but too increase carrying capacity of environment while noble metal adds preparation cost, be unfavorable for commercially producing.The most widely used photochemical catalyst of photocatalyst edman degradation Edman is TiO ₂its stable chemical nature, nontoxic, catalytic activity is high, cost is low, can utilize ultraviolet light that organic matter degradation is become Small molecular, but itself pore structure is undeveloped, attachment point for the thing attachment that is degraded is less, by its with there is the Material cladding enriching pore structure, degraded while can absorption property being improved, be there is actual application value.

Canadian Patent (CA1162904A1) describes a kind of nitrogenous solid organic compounds effectively removing gaseous formaldehyde, by sulfate, have and mix according to a certain percentage compared with the electrodeless alkali of the solid of bigger serface and alkaline organonitrogen compound, inorganic base exists as catalyst, this aminated compounds can with formaldehyde generation chemical reaction, and then effectively remove formaldehyde gas, effect is more remarkable.But because the removal for formaldehyde belongs to chemical reaction, not very desirable to the indoor formaldehyde gas effect of low concentration.

United States Patent (USP) (US 4824577) describes a kind of device removing formaldehyde and phenol in industrial wastewater, first liquid pH to be processed is adjusted to 8, phenol and formaldehyde are fully reacted and produces a large amount of precipitation and ammonia, after removing precipitation, cycle through carbon bed to increase the residual formaldehyde concentration in liquid, the a large amount of ammonia react generated with previous step, is removed.This installation cost is low, and reaction unit is simple, and certain carbon adds can this course of reaction of catalysis, but relates to and regulate pH, adds the difficulty of suitability for industrialized production.

Publication number a kind of sorbing material removing indoor formaldehyde gas that has been the Introduction To Cn Patent of CN102580688A, raw material is a certain proportion of tannin, collagenous fibres and crosslinking agent.Persimmon powder and collagenous fibres joined stirring and dissolving in distilled water, reconciles pH to 6 ~ 7 after adding crosslinking agent, then heating water bath, filter, dry, pulverize the sorbing material obtaining energy absorbing formaldehyde gas.Preparation technology is simple, and cost is low, and absorption property is relatively excellent, but simple adsorbance is limited and there is serious absorption saturation problem.

Composite catalyst of publication number a kind of purifying indoor formaldehyde that has been the Introduction To Cn Patent of CN102198405A and preparation method thereof, with KMnO ₄for raw material, be adsorbed on the carriers such as active carbon powder, carbon fiber powder or molecular sieve by infusion process, by reducing agent MnSO ₄solution and KMnO ₄reaction, generates the MnO of uniform deposition on carrier ₂powder, after by this carrier impregnation in the metal ion solutions such as silver, copper, zinc, rotary evaporation obtains composite catalyst.Formaldehyde gas can be degraded into Small molecular carbon dioxide and water by this method, and catalytic efficiency is higher, but the load of noble metal improves the preparation cost of catalyst.

Publication number has been the Introduction To Cn Patent of CN101337177A, and a kind of energy adsorbs and the application of the active carbon of decomposing formaldehyde.With absorption, all kinds of metal phthalocyanine of covalent bond form complexed load on the active carbon of fibrous activated carbon, granular active carbon, the various shape such as powder activated, charcoal absorption formaldehyde gas, metal phthalocyanine can under the existence having oxygen decomposing formaldehyde.The more difficult load of catalyst metals phthalocyanine that this legal system is standby, and Effective degradability is relatively low, reduces the value of actual production.

Publication number a kind of TiO removing indoor low concentration formaldehyde that has been the Introduction To Cn Patent of CN102266762A ₂the preparation method of-ACF material, by a certain amount of Ti (OC ₄h ₉) ₄join in the ethanol of vigorous stirring, after continuing to stir a period of time, obtain the ethanolic solution A of its dispersion; Separately get a certain amount of ethanol and add water, acetic acid, acetylacetone,2,4-pentanedione, FeCl ₃.6H ₂o, the solution B stirred, dropwise adds B in above-mentioned solution A, leaves standstill, obtains titanium colloidal sol.NACF is put into the rear centrifugation of wherein dipping, dry, high-temperature calcination, obtains TiO ₂-ACF composite, makes full use of high absorption property and the TiO of carbon fiber ₂catalytic degradation performance, but still fail to overcome the fixing problem of traditional catalyst shape, and reactions steps is comparatively loaded down with trivial details, is unfavorable for large-scale commercial applications.

In sum, the method that tradition removes indoor formaldehyde mainly comprises powdered active carbon, block absorbent charcoal, NACF to its direct absorption, or by noble metal, organic compound, MnO ₂even load on the carbon carrier, utilizes the oxygen in air that formaldehyde molecule is degraded into Small molecular.Traditional method often adsorbance is lower, easily saturated, needs to be diligent in changing, and the interpolation of noble metal simultaneously adds cost and the carrying capacity of environment of catalyst preparing, inhibits and commercially produces on a large scale.Polyurethane foam charcoal is the active carbon of a pore structure prosperity that class preparation technology is simple, cost is low, has larger absorption volume, can be prepared into arbitrary shape; TiO ₂be traditional photochemical catalyst, the two compound effectively can be improved the degradation rate of formaldehyde, have actual use value.

Summary of the invention:

The object of the present invention is to provide a kind of preparation method of light degradation formaldehyde cellular activated carbon.

In order to achieve the above object, the technical solution used in the present invention comprises: a kind of preparation method of light degradation formaldehyde cellular activated carbon, it is characterized in that: in homemade glassine paper mould, put into powdered active carbon, stir a period of time after adding black material, add rapidly white material, to its free foaming after high-speed stirred, through room temperature curing aftershaping, be placed in Muffle furnace high-temperature heat treatment, after being cooled to room temperature, namely obtain cellular active carbon, by the TiO of P-25 type ₂nano particle becomes suspension through ultrasonic disperse, is soaked completely by the Alveolate activated carbon capable of preparation, is placed in baking oven heat treatment, and obtained P-25/ absorbent charcoal composite material, embodies under ultraviolet light and have good Photocatalytic Degradation Property to indoor formaldehyde.The main feature of this operating procedure is that method of operating is simple, the Alveolate activated carbon capable specific area of preparation is larger, there is higher absorption property, can arbitrary shape be prepared into, attractive in appearance and be convenient to put, after load P-25, P-25 nano particle is uniformly dispersed in its surface and duct, has good catalytic degradation performance to indoor formaldehyde gas, and reusable, low production cost, is applicable to the removal of formaldehyde gas after house fitting-up.

Advantage of the present invention is:

1, the polyurethane foam charcoal that prepared by the present invention has the advantages such as density is low, intensity is large, pore structure is flourishing, resistance to combustion is high temperature resistant, and every character index can by regulating the amount regulation and control of raw material ratio and active carbon.

2, instant invention overcomes deficiency of the prior art, solve existing Carbon foam and limit to the problems such as the application caused is limited, utilization rate is low by shape, can be made into arbitrary shape, reduce reaction temperature, Reaction time shorten, reaction condition is gentle, process operation is simple, production cost is low, and yield is high, is applicable to large-scale commercial and produces.

3, the present invention is by business photochemical catalyst P-25 nanometer particle load in Carbon foam, overcomes itself absorption property low, the defect that the pollutant attachment point that is degraded is few, solves the problem being difficult to reclaim simultaneously.

4, the P-25/ absorbent charcoal composite material absorption property prepared of the present invention is good, good catalytic degradation performance is had to low concentration formaldehyde under ultra violet lamp, stable in catalytic performance, recyclablely reuses, and is suitable for making handicraft and puts interior decoration formaldehyde gas of degrading at home.

Accompanying drawing illustrates:

Fig. 1 is the SEM picture of the P-25/ absorbent charcoal composite material that the embodiment of the present invention 1 prepares;

Fig. 2 be the P-25/ absorbent charcoal composite material for preparing of the embodiment of the present invention 1 under UV-irradiation to the degradation curve of indoor formaldehyde.

Detailed description of the invention:

Below the invention process is described in further detail:

A kind of preparation method of light degradation formaldehyde cellular activated carbon, it is characterized in that: in homemade glassine paper mould, put into powdered active carbon, a period of time is stirred after adding black material, add rapidly white material, to its free foaming after high-speed stirred, through room temperature curing aftershaping, be placed in Muffle furnace high-temperature heat treatment, namely cellular active carbon is obtained, by the TiO of P-25 type after being cooled to room temperature ₂nano particle becomes suspension through ultrasonic disperse, is soaked completely by the Alveolate activated carbon capable of preparation, is placed in baking oven heat treatment, and obtained P-25/ absorbent charcoal composite material, embodies under ultraviolet light and have good Photocatalytic Degradation Property to indoor formaldehyde.

Below, the present invention will be further detailed by embodiment, but it is not limited to any one or similar example of these embodiments.

Embodiment 1:

The black material of the 10.0g (polyethers 4110 of 5 parts is added in glassine paper mould, the silicone oil that hard bubbles of 0.2 part, the water of 0.08 part, the pentamethyl-diethylenetriamine of 0.006 part, dichloro one fluoroethane of 4 parts, the mixture of the ethylenimine of 0.2 part), 2.0g powdered active carbon, after the rotating speed stirring 60s of 150r/min, add 7.0g to expect in vain, rotating speed brings up to 600r/min to its free foaming, makes it shaping under room temperature after slaking 12h, namely obtains cellular active carbon after being placed in Muffle furnace 350 DEG C of heat treatment 1h.

By the TiO of P-25 type ₂nano particle makes through ultrasonic disperse the suspension that concentration is 1%, above-mentioned cellular active carbon is immersed in a period of time in suspension, is placed in baking oven and is heat-treated to bone dry, obtain P-25/ absorbent charcoal composite material.

Preparation P-25/ absorbent charcoal composite material is suspended in laboratory self-control photocatalytic degradation device, 1 μ L formalin is injected with miniature sampler, open air blast, place 20min to formaldehyde volatilization and adsorption equilibrium, open uviol lamp, the amount of every 20min sampling formaldehyde measurement instrument test residual formaldehyde, until content of formaldehyde is constant, the final degradation rate of PARA FORMALDEHYDE PRILLS(91,95) reaches 80.3%.

Embodiment 2:

The black material of the 10.0g (polyethers 4110 of 6 parts is added in glassine paper mould, the silicone oil that hard bubbles of 0.1 part, the water of 0.08 part, the pentamethyl-diethylenetriamine of 0.008 part, the dichloro monochlorethane of 4 parts, the mixture of the ethylenimine of 0.2 part), 4.0g powdered active carbon, after the rotating speed stirring 50s of 200r/min, add 9.0g to expect in vain, rotating speed brings up to 500r/min to its free foaming, makes it shaping under room temperature after slaking 20h, namely obtains cellular active carbon after being placed in Muffle furnace 450 DEG C of heat treatment 1h.

By the TiO of P-25 type ₂nano particle makes through ultrasonic disperse the suspension that concentration is 1.5%, above-mentioned cellular active carbon is immersed in a period of time in suspension, is placed in baking oven and is heat-treated to bone dry, obtain P-25/ absorbent charcoal composite material.

Preparation P-25/ absorbent charcoal composite material is suspended in laboratory self-control photocatalytic degradation device, 1 μ L formalin is injected with miniature sampler, open air blast, place 20min to formaldehyde volatilization and adsorption equilibrium, open uviol lamp, the amount of every 20min sampling formaldehyde measurement instrument test residual formaldehyde, until content of formaldehyde is constant, the final degradation rate of PARA FORMALDEHYDE PRILLS(91,95) reaches 81.8%.

Claims (8)

1. the preparation method of a light degradation formaldehyde cellular activated carbon, it is characterized in that: in homemade glassine paper mould, put into powdered active carbon, a period of time is stirred after adding black material, add rapidly white material, to its free foaming after high-speed stirred, through room temperature curing aftershaping, be placed in Muffle furnace high-temperature heat treatment, namely cellular active carbon is obtained, by the TiO of P-25 type after being cooled to room temperature ₂nano particle becomes suspension through ultrasonic disperse, is soaked completely by the Alveolate activated carbon capable of preparation, is placed in baking oven heat treatment, and obtained P-25/ absorbent charcoal composite material, embodies under ultraviolet light and have good Photocatalytic Degradation Property to indoor formaldehyde.

2. according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: the black material in raw material refers to the polyethers 4110 of 4 ~ 8 parts, the silicone oil that hard bubbles of 0.1 ~ 0.3 part, the water of 0.08 part, the pentamethyl-diethylenetriamine of 0.005 ~ 0.009 part, dichloro one fluoroethane of 3 ~ 5 parts, the mixture of the ethylenimine of 0.2 part.

3. according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: the white material in raw material refers to methyl diphenylene diisocyanate, black material is 1:1 ~ 5:3 with the mass ratio of expecting in vain.

4., according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: add powdered active carbon amount be 10% ~ 40% of black material and white material mixture.

5., according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: after adding black material, mixing speed is 100 ~ 300r/min, and the time is 30 ~ 60s, and after adding white material, mixing speed is 500 ~ 700r/min.

6., according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: the room temperature curing time is 12 ~ 24h.

7., according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: Muffle furnace high-temperature heat treatment temperature is 300 ~ 500 DEG C, the time is 1 ~ 3h.

8. according to the preparation method of a kind of light degradation formaldehyde cellular activated carbon according to claim 1, it is characterized in that: the suspension concentration of the P-25 nano particle of preparation is 1% ~ 5%.