CN104828823B - NACF skeleton of three-dimensional space net structure and preparation method thereof - Google Patents
NACF skeleton of three-dimensional space net structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses NACF skeleton of a kind of three-dimensional space net structure and preparation method thereof, belong to absorbent charcoal material field.The present invention is with wood fibre and polymeric binder as carbon source, first make and there is multidirectional distribution, be interweaved, intersect the non-woven precast body being bonded to one, then obtain the NACF skeleton of three-dimensional space net structure being fixedly connected by polymeric binder activated carbon through carbonization and activation.Compared with this activated carbon skeleton and existing powdery or granular or activated carbon carbon fiber knitted body, good integrity, voidage are high, absorption affinity is strong, bioaffinity is good, primary raw material comes from reproducible Plant fiber, low cost of manufacture, can be widely used for the fields such as purification of water quality, gas purification, Water Ecological Recovery and catalytic carrier.
Description
Technical field
NACF skeleton of a kind of three-dimensional space net structure according to the present invention and preparation method thereof, belongs to activity
Carbon Materials technical field.
Background technology
Activated carbon is a kind of porous material, and specific surface area is big, high adsorption capacity, acid and alkali-resistance, heat-resisting, water insoluble and have
Machine solvent, is a kind of environmentally friendly adsorbing material and catalyst carrier, be widely used in chemical industry, environmental protection, food processing, metallurgy,
The fields such as military chemistry protection.Activated carbon product form mainly has powdery, graininess and column, generally one-dimensional or two-dimentional knot
Structure, three dimensional structure difficulty of processing is big, and high processing costs are it is difficult to meet the needs of market application.
The activated carbon of three dimensional structure includes active carbon fiber felt and activated carbon establishment body, and CN102641522A discloses " three
The preparation method of dimension gradient netlike carbon fiber/HA/ Maifanitum medical composite material ", this patent of invention is woven into three carbon fiber
Dimension gradient netlike carbon fiber skeleton.Carbon fibe knitted body low production efficiency, the junction point between fiber is not fixedly connected, overall
Property is poor.
Active carbon fibre fiber products processing route mainly includes：Using staple fibre, after carbonization and activation, make activated carbon
The different structures such as fiber felt, cloth, shape and size, this kind of production of articles high cost is it is difficult to make high mechanical strength, large scale multiple
The product of miscellaneous structure；Next to that being supported on activated carbon powder on fiber medium, make the activated carbon of different structure, shape and size
Fibre, there is blockage of the micro orifice, globality poor in this based article, have such problems as de- charcoal and can not clean.
Content of the invention
It is an object of the invention to provide a kind of NACF of the three-dimensional space net structure of low cost, good integrity
Skeleton and preparation method thereof, overcomes the above-mentioned technology that existing one-dimensional, 2 and 3 dimensional organization active carbon fibre fiber products exist not
Foot.
The technical scheme is that：A kind of NACF skeleton of three-dimensional space net structure, this skeleton includes bearing
Carry or do not load the wood activated charcoal fiber with wood fibre as carbon source of catalyst and load or do not load catalyst with polymer
Binding agent is the polymeric binder activated carbon of carbon source, and polymeric binder activated carbon is attached to wood activated charcoal fiber surface,
Connecting portion between NACF is fixedly connected by described polymeric binder activated carbon, and NACF is in three-dimensional many
To distribution, it is interweaved, interconnection becomes an entirety.
Aforesaid NACF includes one or two connected modes following：
（1）Wood activated charcoal fiber is connected in the way of overlapping, and wood activated charcoal fiber connecting portion contacts with each other；
（2）Wood activated charcoal fiber is connected in the way of putting up a bridge, and wood activated charcoal fiber is in space intersection, is not in contact with each other.
A kind of NACF skeleton preparation method of three-dimensional space net structure of the present invention, comprises the following steps：
（1）The non-woven precast body of three-dimensional space net structure makes
Using the polymeric binder of load or not supported activator, activated catalyst, will load or not supported activator,
The wood fibre of activated catalyst is bondd, the three-dimensional space net structure obtaining being bonded to one by polymeric binder
Non-woven precast body, described wood fibre is in that 3 D multi-directional is distributed, and is interweaved, interconnection；
（2）Carbonization and activation processing
Described non-woven precast body is carried out carbonization and activation processing, is loaded or do not load the three dimensions net of catalyst
The NACF skeleton of shape structure.
Aforesaid wood fibre includes one of Petiolus Trachycarpi fiber or bast-fibre and the mixing of two or more fibers
Thing.
Aforesaid wood activated charcoal Fiber Aspect Ratio is 10～500.
Aforesaid polymeric binder includes natural plant starch or resin or rubber or plastics or Colophonium or coal tar.
Compared with the prior art
A kind of NACF skeleton of three-dimensional space net structure that the present invention provides, compared with prior art, has
Three-dimensional space net structure, good integrity, voidage are big, fluid breathability is good, be not easily blocked, not conglomeration, can clean, not fall
Charcoal, easily make labyrinth large scale product, be mainly used in air cleaning, sewage disposal, Water Ecological Recovery and catalytic carrier etc.
Field.
A kind of three-dimensional space net structure NACF skeleton preparation method that the present invention provides, with existing staple fibre
Activated carbon is compared, and raw material sources are wide, belong to Renewable resource, and without artificial spinning, technology controlling and process is simple, low production cost, with
On fiber medium, load type active carbon powder product is compared, and without carrier, product activated carbon content is high.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail.
The invention provides a kind of NACF skeleton of three-dimensional space net structure, this skeleton is with wood fibre and poly-
Compound binding agent is carbon source, including by load or not supported activator, the wood activated charcoal fiber of catalyst and load or do not load
Activator, the polymeric binder activated carbon of catalyst are fixedly connected the three dimensions of integral load or not supported catalyst
Cancellated NACF skeleton.
The NACF skeleton of the three-dimensional space net structure of the present invention, refers to that phosphorus content is more than 50%, BET specific surface
Amass and be more than 120m2/ g, bulk density are 0.1g/cm3～0.5g/cm3NACF skeleton.
The NACF skeleton of the three-dimensional space net structure of the present invention, aforesaid wood activated charcoal fiber and polymer
The mass fraction of binding agent activated carbon is than for 1：（3～0.1）.
The three-dimensional space net structure NACF skeleton of the present invention, aforesaid wood fibre carbon source include mountain monofilament,
Oil palm filaments, coconut fibre silk, Folium Agaves Sisalanae silk, Corchorus olitorius L. silk, lumber fibre silk, bamboo fiber silk one of and two or more mixing
Thing.
The NACF skeleton of the three-dimensional space net structure of the present invention, aforesaid mountain monofilament, oil palm filaments, coconut fibre silk,
Folium Agaves Sisalanae silk and Corchorus olitorius L. silk, are the wooden fibre separated from mountain Rice dumpling leaf, oil palm fruit, Cortex cocois radicis gel, sisal leaves and Corchorus olitorius L. bast respectively
Dimension bundle.
The three-dimensional space net structure NACF skeleton of the present invention, aforesaid polymeric binder carbon source includes natural
Plant amylum, resin, rubber, plastics, Colophonium and coal tar.
Usually, polymeric binder is liquid, and the polymeric binder of the selection of the present invention is additionally included in energy under high temperature
Enough it is melted into the solid binder of liquid, for example, pitch particle, expanded plastic particles and polymer spun fibers etc..
Usually, using liquid polymer binding agent, the NACF skeleton of the present invention will be connected in the way of overlapping.
Usually, using solid polymer binding agent, the NACF skeleton of the present invention will be connected in the way of putting up a bridge.
The invention provides a kind of three-dimensional space net structure NACF skeleton preparation method, comprise the following steps：
First, using the polymeric binder of load or not supported activator, activated catalyst, will load or not load work
Agent, the wood fibre of activated catalyst are bondd, and the three dimensions obtaining being bonded to one by polymeric binder are netted
The non-woven precast body of structure, wood fibre is in that 3 D multi-directional is distributed, and is interweaved, interconnection.
Then, described non-woven precast body is carried out carbonization and activation processing, loaded or do not load the three-dimensional of catalyst
The NACF skeleton of space net structure.
The three-dimensional space net structure NACF skeleton preparation method of the present invention, the netted non-woven of aforementioned three dimensions
Bonding between fiber in precast body and fiber, mainly connected by the bonding agent that the fiber of space intersection is assembled in intersection
's.
The three-dimensional space net structure NACF skeleton preparation method of the present invention, in certain embodiments, including wood
Matter fibrous raw material and the pretreatment of polymeric binder raw material, wherein, wood fibre pretreatment includes cutting back, remove impurity and activator
Mixing etc..
In certain embodiments, the lignocellulose raw material of the present invention needs to moisture content so that fiber has certain volume
Curvature.
In certain embodiments, the lignocellulose raw material of the present invention needs to carry out combing cutting back fibre length, usually, fine
Dimension length is 10mm～350mm, a diameter of 0.1mm～0.6mm.For in principle, the length of wood fibre is shorter, diameter more
Little, the homogeneity of spatial networks NACF skeleton and bulk density higher.
In certain embodiments, the lignocellulose raw material of the present invention needs to carry out remove impurity process, reduce Si in raw material, Al,
The impurity such as Ca, Mg, improve the performance of activated carbon.
In certain embodiments, infusion process is mainly taken in the mixing of the activator of the present invention, ZnCl2Deng activator infiltration
To the inside of wood fibre, usually, dip time is 2～24 hours, 20 DEG C～80 DEG C of solution temperature.
In certain embodiments, the polymeric binder of the present invention needs the aspects such as the viscosity to binding agent, load catalyst
It is modified.
In certain embodiments, a kind of three-dimensional space net structure NACF non-woven precast body of the present invention needs
Shaped or density adjusting is it is preferable that first made tabular, then thermocompression forming adjust density under moulded state.
Aforementioned activation method includes physical activation method, chemical activation method and fly ash method.
In certain embodiments, activator includes KOH, ZnCl2、H3PO4、H2O and CO2.
In certain embodiments, catalyst includes NH4H2PO4、(NH4)2SO4.
In some embodiments it may be preferred that 110 DEG C～500 DEG C of carburizing temperature, 3 DEG C of programming rate～30 DEG C/min, carbonization
Time 0.5h～10h.
In some embodiments it may be preferred that 350 DEG C～1300 DEG C of activation temperature, 3 DEG C of programming rate～30 DEG C/min, live
Change time 0.5h～10h.
In some embodiments it may be preferred that carbonization and activation are carried out continuously.
In certain embodiments, the three-dimensional space net structure NACF skeleton preparation method of the present invention also include right
NACF skeleton carries out pickling, washing, dehydration and modification, obtains the more excellent three-dimensional space net structure activity of performance
Carbon fibe skeleton.
Next, being directed to above-mentioned preparation method, provide several specific embodiments：
Embodiment 1：
By length be 30mm～250mm, solid-liquid ratio 1：3～5 coconut fibre silk, the ZnCl of 60 DEG C of immersion2In solution, dipping 8 is little
When, solution concentration is 50～57 Baume degrees, and pH value is 1.0～3.5, and being dried after centrifuge dripping to moisture content is 15%～20%, obtains
To load ZnCl2The coconut fibre silk of activator；By ZnCl2It is added in natural emulsion aqueous solution, obtain the ZnCl that concentration is 6%2Breast
Glue caking agent；Ready coconut fibre silk is delivered to cyclone separator, by free fall, obtains the fiber that thickness is 30mm
Layer；According to coconut fibre and natural emulsion dry matter weight than for 1:1 glue consumption, ready natural emulsion is uniformly sprayed
To on fibrous layer, coconut fibre silk is bonded to one, is then dried, obtain the coconut fibre felt that moisture content is less than 20%.By 10
The fiber felt of piece 30mm is bondd, and obtains the coconut fibre felt that thickness is 300mm；The coconut fibre felt for 300mm for the thickness is put into mould
In, temperature be 140 DEG C, under the pressure of 15Mpa, static pressure took out after 30 seconds, then trimming, and obtaining density is 0.4g/cm3Three
Dimension space cancellated cylindricality coconut fibre non-woven precast body.
Cylindricality coconut fibre non-woven precast body is put into heating in kiln, programming rate is 10 DEG C/min, is heated to 300
DEG C insulation 20min carry out carbonization；Then proceed to heat, programming rate is 15 DEG C/min, is heated to 650 DEG C and is activated, insulation
Take out after 30min, be cooled to 80 DEG C, obtain the coconut fibre NACF plate of three-dimensional space net structure.By coconut fibre active carbon fibre
Dimension plate put into temperature be 80 DEG C, HCl concentration be 20% dilute hydrochloric acid solution in soak 1 hour, after centrifuge dehydration, continuation clear water rushes
The pH value being washed till water is 5 to 6, obtains the coconut fibre NACF skeleton of three-dimensional space net structure.
Result shows, this NACF skeleton phosphorus content 96%, wood activated charcoal fiber and polymeric binder activated carbon
Mass fraction than for 1：0.4, BET specific surface area 1000m2/g.
This NACF skeleton is applied to NACF water purification catridge.
Embodiment 2：
The oil palm filaments for 30mm～250mm for the length are dried to moisture content 15%～20%；Colophonium is melted, is obtained
To pitch binder.Ready oil palm filaments are delivered to cyclone separator, by free fall, obtain the fibre that thickness is 20mm
Dimension layer；According to oil palm filaments and asphalt quality than for 1:1.5 ratio row consumption, ready pitch binder is uniformly sprayed onto fibre
On dimension layer, fibre bundle is bonded to one.The Elaeis guineensis Jacq. piece for 20mm for the thickness is put under forcing press, is 120 DEG C, 5Mpa in temperature
Pressure under, static pressure 10 seconds, cleaved, obtain density be 0.3g/cm3Oil palm filaments non-woven precast body.
Oil palm filaments non-woven precast body is put in kiln heating, programming rate is 10 DEG C/min, be heated to 450 DEG C～
600 DEG C of insulation 90min carry out carbonization；Then proceed to heat, programming rate is 15 DEG C/min, is heated to 800 DEG C～950 DEG C, even
The continuous overheated steam being passed through 300 DEG C～400 DEG C is activated, and takes out, be cooled to room temperature, obtain space networks after insulation 120min
The Elaeis guineensis Jacq. NACF plate of shape structure.
Elaeis guineensis Jacq. NACF plate is put in the ammonia spirit that temperature is 45 DEG C and soaks 1 hour, after centrifuge dehydration,
It is dried, obtain Elaeis guineensis Jacq. NACF skeleton.
Result shows, this NACF skeleton phosphorus content 93%, wood activated charcoal fiber and polymeric binder activated carbon
Mass fraction than for 1：1.2, BET specific surface area 900m2/g.
This NACF skeleton is applied to membrane bioreactor activated carbon ecological fiber plate.
Embodiment 3：
Folium Agaves Sisalanae is carried out combing, makes the Folium Agaves Sisalanae silk that length is 50mm～100mm；By ready Folium Agaves Sisalanae silk and PP foaming
Granule is delivered to cyclone separator, by free fall, obtains the sisal fiber felt that thickness is 20mm.By the sword for 20mm for the thickness
Flaxen fiber piece is put under forcing press, temperature be 150 DEG C, under the pressure of 0.5Mpa, static pressure 10 seconds, cleaved, obtain density
Sisal fiber precoated plate for 0.2g/cm3.
Sisal fiber precoated plate is put into heating in kiln, programming rate is 10 DEG C/min, be heated to 350 DEG C of insulations
60min carries out carbonization；Then proceed to heat, programming rate is 15 DEG C/min, is heated to 850 DEG C, is continuously passed through high temperature CO 2 gas
Activation, takes out after insulation 60min, is cooled to room temperature.
Result shows, Folium Agaves Sisalanae NACF skeleton phosphorus content 97%, and wood activated charcoal fiber is active with polymeric binder
The mass fraction of charcoal is than for 1：0.1, specific surface area is 1200g/cm3.
This NACF skeleton is applied to airstrainer.
It should be noted that the preparation method adopting in all of step can be carried out by existing equipment.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the NACF skeleton of a kind of three-dimensional space net structure, this skeleton is by the activated carbon loading or not loading catalyst
Fiber is formed by connecting an entirety, and described fiber is in that 3 D multi-directional is distributed, be interweaved, interconnection it is characterised in that：Described
NACF includes the polymeric binder activated carbon with polymeric binder as carbon source and the wood with wood fibre as carbon source
Activated carbon fiber, described polymeric binder activated carbon is attached to described wood activated charcoal fiber surface, described active carbon fibre
The intersection of dimension is fixedly connected by described polymeric binder activated carbon；Described NACF is in curly.
2. the NACF skeleton of three-dimensional space net structure according to claim 1, wherein, described three dimensions net
The NACF skeleton of shape structure is tabular.
3. the NACF skeleton of three-dimensional space net structure according to claim 1, wherein, described wood fibre bag
Include one of mountain monofilament, oil palm filaments, coconut fibre silk, Folium Agaves Sisalanae silk, Corchorus olitorius L. silk, lumber fibre silk, bamboo fiber silk or two or more
Mixture.
4. the NACF skeleton of the three-dimensional space net structure according to claim 1 or 3, wherein, described wooden fibre
The length of dimension is 10-350mm, a diameter of 0.1-0.6 mm.
5. the NACF skeleton of three-dimensional space net structure according to claim 1, wherein, described polymer bonding
Agent is at least one in natural plant starch, resin, rubber, plastics, Colophonium and coal tar.
6. three-dimensional space net structure NACF skeleton as claimed in claim 1 is it is characterised in that described active carbon fibre
Dimension includes one or two connected modes following：
（1）Wood activated charcoal fiber is connected in the way of overlapping, and described wood activated charcoal fiber connecting portion contacts with each other；
（2）Wood activated charcoal fiber is connected in the way of putting up a bridge, and wood activated charcoal fiber is in space intersection, is not in contact with each other.
7. three-dimensional space net structure NACF skeleton preparation method as claimed in claim 1, comprises the steps：
（1）The non-woven precast body of three-dimensional space net structure makes
Using the polymeric binder of load or not supported activator, activated catalyst, will load or not supported activator, activation
The wood fibre of catalyst is bondd, and the non-of three-dimensional space net structure obtaining being bonded to one by polymeric binder is knitted
Thing precast body, described wood fibre is in that 3 D multi-directional is distributed, and is interweaved, interconnection；
The intersection of described wood fibre is fixedly connected by described polymeric binder；Described wood fibre is in curly；
（2）Carbonization and activation processing
Described non-woven precast body is carried out carbonization and activation processing, is loaded or do not load the described three dimensions net of catalyst
The NACF skeleton of shape structure.
8. three-dimensional space net structure NACF skeleton preparation method according to claim 7 is it is characterised in that institute
State wood fibre and include one of Petiolus Trachycarpi fiber or bast-fibre and two or more fibre blends.
9. three-dimensional space net structure NACF skeleton preparation method according to claim 7 is it is characterised in that institute
Stating wood activated charcoal Fiber Aspect Ratio is 10～500.
10. three-dimensional space net structure NACF skeleton preparation method according to claim 7 it is characterised in that
Described polymeric binder includes natural plant starch or resin or rubber or plastics or Colophonium or coal tar.
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| CN105667004B (en) * | 2016-01-29 | 2017-11-17 | 方存仁 | A kind of method in situ for eliminating ski dome |
| JP6603005B2 (en) * | 2017-09-29 | 2019-11-06 | 積水化学工業株式会社 | Reinforced fiber bundle, reinforced fiber spread fabric, fiber reinforced composite, and production method thereof |
| CN107804845A (en) * | 2017-11-03 | 2018-03-16 | 华南农业大学 | A kind of level hole carbon block material for purifying formaldehyde and its preparation method and application |
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| CN110917726B (en) * | 2019-12-12 | 2021-10-22 | 上海科格思过滤材料有限公司 | Preparation method of novel frameless filter material |
| CN111762771A (en) * | 2020-07-10 | 2020-10-13 | 山东理工大学 | Self-welding process of high-length-diameter-ratio fiber carbon |
| CN111924824B (en) * | 2020-08-14 | 2023-02-17 | 山东理工大学 | Preparation method of carbon with high specific surface area and high conductivity |
| CN112142049A (en) * | 2020-09-14 | 2020-12-29 | 广东净境环保股份有限公司 | Method for preparing fiber adsorption material by using waste fabric |
| CN113024035B (en) * | 2021-03-16 | 2021-12-07 | 扬州工业职业技术学院 | Printing and dyeing wastewater treatment device and system |
| CN113735116B (en) * | 2021-09-29 | 2023-02-10 | 中钢集团鞍山热能研究院有限公司 | Method for regulating and controlling high vitrinite caking coal-based activated carbon structure by textile waste |
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| EP2072463A4 (en) * | 2006-10-12 | 2013-08-14 | Cataler Corp | Active carbon, and canister and intake air filter utilizing the same |
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| CN1537075A (en) * | 2001-04-11 | 2004-10-13 | 米德韦斯特瓦科公司 | Shaped activated carbon |
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