CN107399928A - A kind of glass fibre ball beam and preparation method thereof - Google Patents
A kind of glass fibre ball beam and preparation method thereof Download PDFInfo
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- CN107399928A CN107399928A CN201710725455.3A CN201710725455A CN107399928A CN 107399928 A CN107399928 A CN 107399928A CN 201710725455 A CN201710725455 A CN 201710725455A CN 107399928 A CN107399928 A CN 107399928A
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- glass fibre
- ball beam
- fibre ball
- preparation
- ether
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
Abstract
The invention discloses a kind of glass fibre ball beam and preparation method thereof, it is included：Step 1, abandoned printed circuit board is crushed, sorted, obtain non-metal powder；Step 2, non-metal powder is added in inorganic acid, 50~95 DEG C of 8~40h of reaction；Step 3, filter, collect glass fibre powder solid and filtrate respectively；Step 4, filtrate is extracted with extractant, is recycled epoxy resin；Step 5, glass fibre powder, recovery epoxy resin press 100：0.1~10 part by weight, it is added under stirring in Amine Solutions, 0.5~30h is reacted at 40~80 DEG C, filtering, obtains glass fibre ball beam.The method of the present invention not only avoid harm of the glass fiber dust to human body during recovery glass fibre and processing, recycling, and the glass fibre ball beam of recovery can be as the carrier of catalyst, nano material and other materials, it can also directly prepare composite, the reduction of the performance caused by high temperature during extruding pelletization is avoided, is had a good application prospect.
Description
Technical field
The present invention relates to the recovery of glass fibre in abandoned printed circuit board non-metal powder, and in particular to a kind of glass fibre
Ball beam and preparation method thereof.
Background technology
Printed circuit board (PCB) (Printed Circuit Boards, abbreviation PCB) is the most basic component of electronic product, is
The basis that each component is connected with each other in electronic product.Common household electrical appliance are mainly TV in our daily lifes
Machine, washing machine, refrigerator, air-conditioning and computer.In recent years, these household electrical appliance have been enter into the peak period eliminated and scrapped.These
Contain substantial amounts of printed substrate in household electrical appliances.With being continuously increased for discarded household appliances quantity, discarded PCB amount also increases year by year
Add.
Except from electronic waste beyond the region of objective existence, it is exactly caused corner in PCB production processes that discarded PCB, which also has a source,
Material and defective work.Leftover pieces and defective work constitute about the 10~20% of PCB productions.China is printed circuit board (PCB)
Big producer, thus the leftover pieces and defective work of substantial amounts will be produced every year.
Contain substantial amounts of metal in discarded PCB, there is the recovery that many enterprises are engaged in metal in discarded PCB.By disassembling,
The steps such as broken, sorting, can recycle most metal recovery, and remaining non-metal powder turns into secondary pollution, greatly
Amount is deposited in some corner.
Landfill and burning are the conventional methods for handling these thermosetting epoxy resin discarded objects on a large scale.Landfill does not only take up
Valuable land resource, and pollute the environment.Contain heavy metal and brominated flame retardant in some thermosetting epoxy resin discarded objects
Agent (such as abandoned printed circuit board non-metal powder), these heavy metals and brominated flame retardant can be leached and contaminated soil and ground by rainwater
Lower water etc..Burning can produce substantial amounts of clinker, and the discarded object containing brominated flame retardant is burning (such as discarded PCB non-metal powders)
When can produce substantial amounts of noxious material, particularly more bromo dibenzo dioxin and PBDF.
Contain substantial amounts of glass fibre in these non-metal powders, account for the 70% of weight.In patent CN101407596B
The method for disclosing glass fibre in a kind of chemical method recovery abandoned printed circuit board non-metal powder.This method reclaims what is obtained
Glass fibre is white powder, in processing and is also easy to produce airborne dust during using these glass fibre powder, into respiratory tract and eyes,
Particularly easily prick into skin, do harm to huamn body, cause discomfort.In order to improve the harm of glass fiber powder, the present invention is public
A kind of preparation method of glass fibre ball beam of cloth, by glass fiber powder glomeration beam, avoids the harm of glass fiber powder.
The content of the invention
It is an object of the invention to provide a kind of glass fibre ball beam is prepared by abandoned printed circuit board for raw materials recovery
Method, on the one hand glass fibre that this method has been reclaimed in abandoned printed circuit board non-metal powder is allowed to be recycled, another
Aspect avoids harm of the glass fiber dust to human body during recovery glass fibre and processing, recycling.
In order to achieve the above object, the invention provides a kind of preparation method of glass fibre ball beam, it is included：
Step 1, abandoned printed circuit board is crushed, sorted, obtain non-metal powder；
Step 2, non-metal powder made from step 1 is added in inorganic acid, is heated to 50~95 DEG C, reaction 8~40 is small
When；Wherein, the weight of non-metal powder：The volume of inorganic acid is 1g：3~10mL, the concentration of inorganic acid is 3~8mol/L；
Step 3, filter, collect glass fibre powder solid and filtrate respectively；
Step 4, filtrate is extracted using extractant, is removed extractant, is recycled epoxy resin；
Step 5, the obtained recovery epoxy resin of glass fibre powder step 3 collected, step 4 is by 100：(0.1~
10) part by weight, it is added in Amine Solutions under stirring, is reacted 0.5~30 hour at 40~80 DEG C, filtering, obtains glass
Glass fibrous nodules beam；The effect of described organic amine is so that glass fiber powder balling-up beam, selects ethylenediamine, hexamethylene diamine, divinyl
One or both of triamine, triethylene tetramine, diethylaminopropylamine, dipropylenetriamine.
It is preferred that the inorganic acid described in step 2 selects the mixing of one or both of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
Inorganic acid is wrapped in the thermosetting epoxy resin that glass fibre shows, makes glass fibre separate out as distintegrant, decomposition.
It is preferred that solvent selection ether, butyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol third described in step 4
One or more combinations in ether, butyl glycol ether, methyl acetate, ethyl acetate, the fat of acetic acid third, butyl acetate.
It is preferred that step 3 also includes：Washing step using detergent to glass fibre powder solid.
It is preferred that described detergent selection ether, butyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol propyl ether, second
One or more combinations in glycol butyl ether, methyl acetate, ethyl acetate, the fat of acetic acid third, butyl acetate.
It is preferred that in step 5, the gross weight of glass fiber powder and recovery epoxy resin：The volume of Amine Solutions is 1g：
3~30mL.
It is preferred that the concentration of Amine Solutions is 1~30%, by weight percentage.
It is preferred that the solvent of Amine Solutions is ethyl acetate, the fat of acetic acid third, butyl acetate, methyl acetate, ethanol, first
One or more combinations in alcohol, propyl alcohol, isopropanol, acetone.
It is preferred that step 5 also includes the cleaning step using cleaning agent to glass fibre ball beam, to remove glass fibre ball
The resin of beam remained on surface：Glass fibre ball beam is added in cleaning agent, in 35~90 DEG C, stirred 1~20 hour, filtering,
The w/v of collection glass fibre ball beam, glass fibre ball beam and cleaning agent is 1：(3~8) g/mL, the cleaning agent are
One or more in water, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, ethanol, methanol, propyl alcohol, ethyl acetate, the fat of methyl acetate acetic acid third
Combination.
Present invention also offers the glass fibre ball beam that a kind of preparation method of above-mentioned glass fibre ball beam obtains, the glass
Glass fibrous nodules beam can be not only used for the preparation of composite, and can be as catalyst, nano material and other materials
Carrier.
The present invention compared with prior art, has advantages below：
1. the method for the present invention prepares glass fibre ball beam, glass fibre is avoided in recovery, processing and recycles process
In caused glass fiber dust pollution environment and be detrimental to health.
2. glass fibre ball beam prepared by the present invention, has certain surface area as ball beam, is easier to adsorb some nanometers
Or polar material, such as adsorption and oxidation graphene etc., so, can as the carrier of catalyst, nano material and other materials,
Expand the purposes of recovery glass fibre powder.
3. glass fibre ball beam prepared by the present invention can directly be molded into product with high polymer material, extruding pelletization is saved
Link, influence of the extruding pelletization link to properties of product is avoided, at the same it is also cost-effective.Prepared by the present invention has suitable size
Glass fibre ball beam, easily uniformly mix, can directly be molded with plastic grain, can also be direct with the resin such as epoxy resin
It is mixed with same with thermosetting compound material.And then easily accumulation is not easy to disperse glass fibre powder, easy to operate, easy airborne dust etc. is not allowed yet
Characteristic, glass fiber powder is set to disperse in the composite uneven and inconvenient for operation.
4. the inorganic acid used in the present invention recycles, secondary pollution is not caused.
Brief description of the drawings
Fig. 1 is the exterior appearance figure of the glass fibre ball beam of the present invention.
Embodiment
Technical scheme is described further below in conjunction with drawings and examples.
Embodiment 1
By abandoned printed circuit board by crushing and sorting, non-metal powder is collected.100g non-metal powders are taken to be added to 300mL
In 6mol/L salpeter solution, 85 DEG C are heated 20 hours, filtering, the extraction of filtrate spent glycol ether, solid spent glycol ether
Washing, obtains glass fiber powder；Merge ethylene glycol ethyl ether extract and cleaning solution, ethylene glycol ethyl ether boiled off with Rotary Evaporators,
It is recycled epoxy resin.
Glass fiber powder 50g is taken, reclaims epoxy resin 1g, is added to the diethyl of 200mL 6% (by weight percentage)
In the ethanol solution of alkene triamine, 50 DEG C are heated 7 hours, filtering, obtain glass fibre ball beam, then add glass fibre ball beam
Into 150mL ethanol, 40 DEG C are heated 5 hours, are filtered, and are dried, are obtained glass fibre ball beam as shown in Figure 1.
Embodiment 2
By abandoned printed circuit board by crushing and sorting, non-metal powder is collected.130g non-metal powders are taken to be added to 910mL
8mol/L nitric acid and phosphoric acid solution (presses volume 3：1) in, 80 DEG C are heated 10 hours, and filtering, filtrate is extracted with ethyl acetate, Gu
Body is washed with ethyl acetate, obtains glass fiber powder；Combined ethyl acetate extract and cleaning solution, second is boiled off with Rotary Evaporators
Acetoacetic ester, it is recycled epoxy resin.
Take glass fiber powder 50g, reclaim epoxy resin 3g, be added to 230mL 9% (by weight percentage) oneself two
In the propanol solution of amine, 60 DEG C are heated 6 hours, filtering, are obtained glass fibre ball beam, are then added to glass fibre ball beam
In 150mL4M nitric acid, 50 DEG C are heated 3 hours, are filtered, and are dried.
Embodiment 3
By abandoned printed circuit board by crushing and sorting, non-metal powder is collected.120g non-metal powders are taken to be added to 720mL
6mol/L nitric acid and sulfuric acid solution (presses volume 4：1) in, 83 DEG C are heated 12 hours, filtering, filtrate n-butyl acetate extraction, Gu
Body is washed with butyl acetate, obtains glass fiber powder；Merge n-butyl acetate extraction liquid and cleaning solution, second is boiled off with Rotary Evaporators
Acid butyl ester, it is recycled epoxy resin.
Glass fiber powder 50g is taken, reclaims epoxy resin 0.5g, is added to the second of 200mL 15% (by weight percentage)
In the methanol solution of diamines, 60 DEG C are heated 6 hours, filtering, are obtained glass fibre ball beam, are then added to glass fibre ball beam
(volume 3 is pressed in 150mL4M nitric acid and phosphoric acid solution：1), 60 DEG C are heated 10 hours, are filtered, and are dried.
In summary, the present invention by abandoned printed circuit board through crush, sort and remaining non-metal powder in mineral acid
Filtered after heating certain time, obtain glass fiber powder, epoxy resin is reclaimed from filtrate with extraction；By glass fiber powder and
The epoxy resin of recovery adds agitating and heating in Amine Solutions, filtering, obtains glass fibre ball beam；Finally by glass fibre ball
Beam is added in appropriate cleaning agent and heated, and removes the resin of glass fibre ball beam remained on surface, is dried, is obtained glass fibre ball
Beam.The glass fibre ball beam can be not only used for the preparation of composite, be also used as catalyst, nano material and other materials
The carrier of material.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of preparation method of glass fibre ball beam, it is characterised in that this method includes：
Step 1, abandoned printed circuit board is crushed, sorted, obtain non-metal powder；
Step 2, non-metal powder made from step 1 is added in inorganic acid, is heated to 50~95 DEG C, reacted 8~40 hours；Its
In, the weight of non-metal powder：The volume of inorganic acid is 1g：3~10mL, the concentration of inorganic acid is 3~8mol/L；
Step 3, filter, collect glass fibre powder solid and filtrate respectively；
Step 4, filtrate is extracted using extractant, is removed extractant, is recycled epoxy resin；
Step 5, the obtained recovery epoxy resin of glass fibre powder step 3 collected, step 4 is by 100：0.1~10 weight
Amount ratio, it is added in Amine Solutions under stirring, is reacted 0.5~30 hour at 40~80 DEG C, filtering, obtains glass fibre ball
Beam；Described organic amine selects ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine, two propylene three
One or both of amine.
2. the preparation method of glass fibre ball beam as claimed in claim 1, it is characterised in that the inorganic acid choosing described in step 2
Select the mixing of one or both of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
3. the preparation method of glass fibre ball beam as claimed in claim 1, it is characterised in that the extractant choosing described in step 4
Select ether, butyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, methyl acetate, ethyl acetate, second
One or more combinations in sour third fat, butyl acetate.
4. the preparation method of glass fibre ball beam as claimed in claim 1, it is characterised in that step 3 also includes：Using washing
Washing step of the agent to glass fibre powder solid.
5. the preparation method of glass fibre ball beam as claimed in claim 4, it is characterised in that described detergent selection second
Ether, butyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, methyl acetate, ethyl acetate, acetic acid third
One or more combinations in fat, butyl acetate.
6. the preparation method of glass fibre ball beam as claimed in claim 1, it is characterised in that in step 5, glass fiber powder and
Reclaim the gross weight of epoxy resin：The volume of Amine Solutions is 1g：3~30mL.
7. the preparation method of glass fibre ball beam as claimed in claim 6, it is characterised in that the concentration of Amine Solutions is 1
~30%, by weight percentage.
8. the preparation method of glass fibre ball beam as claimed in claim 7, it is characterised in that the solvent of Amine Solutions is second
One or more groups in acetoacetic ester, the fat of acetic acid third, butyl acetate, methyl acetate, ethanol, methanol, propyl alcohol, isopropanol, acetone
Close.
9. the preparation method of glass fibre ball beam as claimed in claim 1, it is characterised in that step 5 is also included using cleaning
Cleaning step of the agent to glass fibre ball beam：Glass fibre ball beam is added in cleaning agent, in 35~90 DEG C, stirring 1~20
Hour, filtering, collect glass fibre ball beam, the weight of glass fibre ball beam：The volume of cleaning agent is 1g：3~8mL is described clear
Lotion is one kind in water, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, ethanol, methanol, propyl alcohol, ethyl acetate, the fat of methyl acetate acetic acid third
Or multiple combinations.
10. the glass fibers that a kind of preparation method of the glass fibre ball beam in 1-9 according to claim described in any one obtains
Tie up ball beam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710725455.3A CN107399928B (en) | 2017-08-22 | 2017-08-22 | Glass fiber ball bundle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710725455.3A CN107399928B (en) | 2017-08-22 | 2017-08-22 | Glass fiber ball bundle and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107399928A true CN107399928A (en) | 2017-11-28 |
| CN107399928B CN107399928B (en) | 2020-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710725455.3A Active CN107399928B (en) | 2017-08-22 | 2017-08-22 | Glass fiber ball bundle and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138645A (en) * | 2020-11-02 | 2020-12-29 | 上海第二工业大学 | Glass fiber ball beam supported GO/TiO2Photocatalyst and preparation method thereof |
| CN112808240A (en) * | 2021-02-08 | 2021-05-18 | 上海第二工业大学 | Glass fiber ball bundle GO/ZIF-8 loaded composite material and preparation method thereof |
| CN114377706A (en) * | 2022-01-04 | 2022-04-22 | 上海第二工业大学 | MXene/TiO loaded by glass fiber ball bundle2Aerogel composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407596A (en) * | 2008-09-25 | 2009-04-15 | 上海第二工业大学 | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board |
-
2017
- 2017-08-22 CN CN201710725455.3A patent/CN107399928B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407596A (en) * | 2008-09-25 | 2009-04-15 | 上海第二工业大学 | Method for recycling epoxy resins and glass fibre from non-metal powder of waste printed circuit board |
Non-Patent Citations (1)
| Title |
|---|
| 王绍文等: "《环保设备材料手册》", 30 September 1992, 冶金工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138645A (en) * | 2020-11-02 | 2020-12-29 | 上海第二工业大学 | Glass fiber ball beam supported GO/TiO2Photocatalyst and preparation method thereof |
| CN112808240A (en) * | 2021-02-08 | 2021-05-18 | 上海第二工业大学 | Glass fiber ball bundle GO/ZIF-8 loaded composite material and preparation method thereof |
| CN114377706A (en) * | 2022-01-04 | 2022-04-22 | 上海第二工业大学 | MXene/TiO loaded by glass fiber ball bundle2Aerogel composite material and preparation method thereof |
| CN114377706B (en) * | 2022-01-04 | 2024-03-12 | 上海第二工业大学 | Glass fiber ball bundle loaded MXene/TiO 2 Aerogel composite material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN107399928B (en) | 2020-03-17 |
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