CN105837854A - Method for manufacturing adsorption separation material from waste old rigid polyurethane foam - Google Patents
Method for manufacturing adsorption separation material from waste old rigid polyurethane foam Download PDFInfo
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- CN105837854A CN105837854A CN201510015625.XA CN201510015625A CN105837854A CN 105837854 A CN105837854 A CN 105837854A CN 201510015625 A CN201510015625 A CN 201510015625A CN 105837854 A CN105837854 A CN 105837854A
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention discloses a method for manufacturing an adsorption separation material from waste old rigid polyurethane foamed plastics. The adsorption separation material is manufactured by putting waste old rigid polyurethane foam in a pulverizer, performing pulverization to obtain powdery foam particles, removing impurities from the powdery foam particles through separation, and putting the rigid foam particles with impurities removed in a basic medium at a certain temperature for degradation. The method is simple in process, mild in reaction conditions, and low in cost. The method enables waste to be utilized and is eco-friendly. The recycling method of waste old rigid polyurethane foam enables efficient and green cyclic utilization of waste old rigid polyurethane foamed plastics to be realized. The manufactured adsorption separation material can be applied to fields, such as purification and separation, wastewater treatment, and fillers.
Description
Technical field
The invention belongs to the regenerative use technology field that waste polyurethane hard bubbles, the method particularly relating to be crushed by physics and chemical degradation combines is hard bubbled by waste polyurethane and is prepared adsorption and separation material.
Background technology
Polyurethane rigid foam plastic is a kind of highly cross-linked thermosets.Hard polyurethane foam mostly is hole-closing structure, there is the good characteristics such as insulation effect is good, lightweight, specific strength big, easy construction, the most also there is the feature such as sound insulation, shockproof, electric insulation, heat-resisting, cold-resistant, solvent resistant, it is widely used in the adiabators such as refrigerator, the casing heat insulation layer of refrigerator-freezer, freezer, refrigerator car, building, storage tank and pipe insulation material, a small amount of for nonadiabatic occasion, such as imitation wood material, packaging material etc..It is said that in general, more low-density hard polyurethane foam is mainly used as heat insulation (insulation) material, the hard polyurethane foam of higher density can be used as structural material.Use widely due to polyurethane rigid foam plastic result also in the appearance (waste material and leftover pieces) of a large amount of hard polyurethane foam garbage.These waste polyurethanes hard bubble and not only result in the waste of resource, are also easy to cause environmental pollution, therefore to the recovery of hard polyurethane foam be treated as problem in the urgent need to address.
It is, in general, that the recycling of RPUF has following several method: heat energy method is reclaimed in physical pulverization method, chemical degradation method and burning.The poor-performing of the product that waste polyurethane rigid foam waste material is made through physical pulverization method, can only make low-grade articles for use and use.It is seemingly best that chemical degradation method reclaims raw material, but degradation reaction is complicated, and product component is complicated, it is difficult to separating effective ingredient.Process waste polyurethane hard bubbles and uses most still burnings to reclaim heat energy method at present.Owing to burning can produce substantial amounts of harmful gas, some polyurethanes hard bubbles will be by dangerous waste disposal, so special incinerator should be used, process takes explosion-proof, fire-retardant measure, the infringement caused environment with minimizing.
Polyurethane open cell foamed plastic has in loose structure, big specific surface area, its molecule and has substantial amounts of polar group, such as carbonyl (＞ C=O) and imino group (＞ N H) etc..Therefore, polyurethane foamed material can realize the active adsorption to metal ion, Organic substance etc. by the various ways such as Van der Waals force, hydrogen bond.Additionally, the ehter bond pair of the polyurethane molecular Organic substance miscible with ether solvent also has good adsorption effect, can be as adsorbent organic concentration and separation process in water environment.Patent CN103071467 proposes a kind of heavy metals trapping material utilizing waste polyurethane sponge to prepare and preparation method.The polyurethane sponge used in this patent belongs to soft polyurethane foam, is the polyurethane foam plastics of a kind of open cell type.
The polyurethane foam being used for preparing adsorbing material at present is typically open-celled structure, and polyurethane rigid foam plastic major part is all hole-closing structure.How being hard bubbled by waste polyurethane according to the feature of polyurethane rigid foam material and the feature of adsorption and separation material and being converted into adsorption and separation material is a significant problem.
Summary of the invention
It is an object of the invention to provide a kind of method preparing adsorption and separation material of being hard bubbled by waste polyurethane.
The method that in the present invention, and chemical degradation broken by physics combines is hard bubbled by waste polyurethane and is prepared adsorption and separation material；Present invention process is simple, reaction condition is gentle, low cost, both twice laid, again environmental protection.The regeneration method that in the present invention, waste polyurethane hard bubbles achieves efficient, the green circulatory of waste polyurethane rigid foam and utilizes, and the adsorption and separation material produced can be applicable to the fields such as purifies and separates, waste water process, filler.
This technical scheme of being proposed of invention is: is hard bubbled by waste polyurethane and prepares adsorption and separation material through pulverizing, remove impurity, alkaline degradation three step:
(1) waste polyurethane rigid foam is put in high speed shear disintegrating machine it is ground into powder and hard bubbles granule；
(2) powder is hard bubbled granule separating and removing impurities；
(3) the hard polyurethane foam granule after the removal of impurity being gone join mass concentration be 1～50% alkali liquor in (hard polyurethane foam amount of particles is the 1～50% of alkali liquor quality), control temperature be 20～80 DEG C, under agitation alkalization degraded 0.1～3h；Filter after completion of the reaction, be successively dried behind 1～the acetic acid of 10%, water washing, obtain adsorption and separation material finished product.
The broken step that in the present invention, waste polyurethane hard bubbles requires that hard polyurethane foam granular powder is broken to below 20 mesh, and optimum is below 100 mesh；
The alkali that in the present invention, alkaline degradation one step is selected is KOH, NaOH, CH3COOK、CH3In COONa a kind；The medium selected is 1 in water, methanol, ethanol, ethylene glycol, isopropanol, glycerol～2 kind.
How being hard bubbled by waste polyurethane and being converted into open-celled structure is the key issue affecting hard polyurethane foam absorption property.The average diameter of major part hard polyurethane foam abscess is between 100～200 μm.The technology of the present invention first makes the average diameter of its fragment realize the hole-closing structure of hard polyurethane foam is converted into open-celled structure in grade, the mode in conjunction with chemical bases degraded with high-speed shearing machine physical pulverization hard polyurethane foam.
Alkaline degradation is in addition to can reducing the particle diameter of hard polyurethane foam granule, perforate, it is also possible to introduce activity primary amino radical at hard polyurethane foam particle surface.The main functional group of hard polyurethane foam is carbamate and urea, and in reaction medium, the equation of alkaline degradation is as shown in Equation 1 for it.Primary amino radical can be with a lot of acidic actives or metal ion generation chemical bonding effect as the group that character is active, and the increase of primary amino radical improves the absorption property of hard polyurethane foam granule.
The alkaline degradation signal of formula 1 hard polyurethane foam
The present invention combines a process difficult problem that waste polyurethane hard bubbles and polyurethane open cell foam material and has the feature of good adsorption properties, first carries out physics by hard bubbling waste polyurethane and crushes perforate and prepare hard polyurethane foam adsorbing material with chemical bases degraded mode further perforate modification the most again.The waste polyurethane being easily generated environmental pollution is hard bubbled and is prepared as adsorption and separation material by the technology of the present invention; this is to solve hard polyurethane foam leftover bits handling problems to provide an economically viable approach, the most alternatively environmental conservation, the field such as separating-purifying of active substance to provide a kind of novel inexpensive adsorption and separation material.
Detailed description of the invention: the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1: waste polyurethane foam high speed shear disintegrating machine is pulverized, crosses 100 mesh sieves, be dried to constant weight at 80 DEG C after ion.
Polyurethane foam 5g pulverized is added in the NaOH aqueous solution of 50mL 20～the 1 of 80 DEG C～50%, after stirring one timing 0.1～3hr, sucking filtration and successively with 1～10% acetum and water wash after dry, obtain adsorption and separation material finished product.
Embodiment 2-4: method is with embodiment 1, the most respectively with KOH, CH3COOK、CH3The NaOH in a kind of alternate embodiment 1 in COONa, respectively obtains corresponding adsorption and separation material.
Embodiment 5-24: with 1 in water, methanol, ethanol, ethylene glycol, isopropanol, glycerol～2 kind of water replaced in embodiment 1 in NaOH aqueous solution respectively, other conditions, with embodiment 1, obtain corresponding adsorption and separation material.
Embodiment 25-44: with 1 in water, methanol, ethanol, ethylene glycol, isopropanol, glycerol～2 kind of water replaced in embodiment 2 in KOH aqueous solution respectively, other conditions, with embodiment 2, obtain corresponding adsorption and separation material.
Embodiment 45-64: replace CH in embodiment 3 respectively with 1 in water, methanol, ethanol, ethylene glycol, isopropanol, glycerol～2 kind3Water in COOK aqueous solution, other conditions, with embodiment 3, obtain corresponding adsorption and separation material.
Embodiment 65-84: replace CH in embodiment 4 respectively with 1 in water, methanol, ethanol, ethylene glycol, isopropanol, glycerol～2 kind3Water in COONa aqueous solution, other conditions, with embodiment 4, obtain corresponding adsorption and separation material.
Embodiment 85: the adsorption and separation material obtained by embodiment 1, measuring its nitrogen content is 0.94%, and primary amino radical content is 0.019mmol/g；Above-mentioned adsorption and separation material is (T=25 DEG C, pH=9.36) absorption 3hr in the Congo red solution of 4g/L, and the adsorbance of Congo red be can reach 1.45g/g.
Claims (4)
1. hard bubbled by waste polyurethane the method preparing adsorption and separation material, it is characterized in that: comprise the following steps: successively
(1) waste polyurethane rigid foam is put in disintegrating machine it is ground into powder and hard bubbles granule；
(2) powder is hard bubbled granule separating and removing impurities；
(3) by 1～50% go the removal of impurity after hard polyurethane foam granule join mass concentration be 1～50% alkali liquor in, control temperature be 20～80 DEG C, under agitation alkalization degraded 0.1～3h；Filter after completion of the reaction, be successively dried behind 1～the acetic acid of 10%, water washing, obtain adsorption and separation material finished product.
The most according to claim 1, hard bubbled by waste polyurethane the method preparing adsorption and separation material, it is characterized in that: in step (1), hard polyurethane foam granular powder is broken to below 20 mesh, optimum is below 100 mesh.
Hard bubbled by waste polyurethane the most according to claim 1 the method preparing adsorption and separation material, it is characterized in that: the alkali selected in step (3) is KOH, NaOH, CH3COOK、CH3In COONa a kind.
Hard bubbled by waste polyurethane the most according to claim 1 the method preparing adsorption and separation material, it is characterized in that: the alkaline degradation medium selected in step (3) is 1 in water, methanol, ethanol, ethylene glycol, isopropanol, glycerol～2 kind.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510015625.XA CN105837854A (en) | 2015-01-13 | 2015-01-13 | Method for manufacturing adsorption separation material from waste old rigid polyurethane foam |
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| CN201510015625.XA CN105837854A (en) | 2015-01-13 | 2015-01-13 | Method for manufacturing adsorption separation material from waste old rigid polyurethane foam |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286369A (en) * | 2017-08-02 | 2017-10-24 | 江苏世丰新材料有限公司 | A kind of method that acidolysis soft polyurethane foam discarded object generates polyalcohol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096426A (en) * | 2007-06-18 | 2008-01-02 | 林永飞 | Method for recycling waste hard foam polyurethane plastic |
| CN103754869A (en) * | 2014-01-02 | 2014-04-30 | 上海大学 | Method for preparing high-quality active carbon by adopting waste polyurethane foamed plastic |
| CN104327300A (en) * | 2014-11-10 | 2015-02-04 | 镇江中化聚氨酯工业设备有限公司 | Alkaline hydrolysis processing technology of polyurethane wastes |
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- 2015-01-13 CN CN201510015625.XA patent/CN105837854A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096426A (en) * | 2007-06-18 | 2008-01-02 | 林永飞 | Method for recycling waste hard foam polyurethane plastic |
| CN103754869A (en) * | 2014-01-02 | 2014-04-30 | 上海大学 | Method for preparing high-quality active carbon by adopting waste polyurethane foamed plastic |
| CN104327300A (en) * | 2014-11-10 | 2015-02-04 | 镇江中化聚氨酯工业设备有限公司 | Alkaline hydrolysis processing technology of polyurethane wastes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286369A (en) * | 2017-08-02 | 2017-10-24 | 江苏世丰新材料有限公司 | A kind of method that acidolysis soft polyurethane foam discarded object generates polyalcohol |
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