CN106832591A - A kind of biomass composite of oil-tea camellia husks base and preparation method thereof - Google Patents
A kind of biomass composite of oil-tea camellia husks base and preparation method thereof Download PDFInfo
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- CN106832591A CN106832591A CN201710124133.3A CN201710124133A CN106832591A CN 106832591 A CN106832591 A CN 106832591A CN 201710124133 A CN201710124133 A CN 201710124133A CN 106832591 A CN106832591 A CN 106832591A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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Abstract
The invention discloses a kind of biomass composite, biomass composite include being formed by modified oil-tea camellia husks powder and polypropylene composite materials, the weight/mass percentage composition of biomass composite that accounts for of modified oil-tea camellia husks powder be 30% 70%.With oil-tea camellia husks as raw material, first after crushed through NaOH solution pretreatment, pulverizer, coupling ethanol solution modification and polypropylene mixing, hot-forming obtain the good biomass composite of mechanical property.The advantages of inexpensive, renewable oil-tea camellia husks, abundance being played by the present invention and concentrated, change the wasting of resources in the past, the utilization ways of pollution environment, wooden resource disparities between supply and demand are alleviated to China and environmental pollution increasingly serious problems could be made that significant contribution.
Description
Technical field
Utilize field the invention belongs to agriculture and forestry organic waste material, particularly belong to oil-tea camellia husks utilize field, more particularly to one kind with
Biomass composite that oil-tea camellia husks are prepared for raw material and preparation method thereof.
Background technology
Cut-off in November, 2013, China's camellia oleifera lam gross area up to 57,500,000 mu, about 450,000 tons of tea oil annual production, the output value is high
Up to 39,000,000,000 yuan.Oil-tea camellia husks process one of byproduct of tea oil as oil tea, account for the 50%~60% of tea fruit fresh weight.Past,
Oil-tea camellia husks be often taken as discarded object directly using burn etc. extensive style processing mode, not only caused the serious wasting of resources but
Environment is polluted to a certain extent.In face of enriching considerable biomass resource, country promulgates a series of policies and file successively, clearly
The importance of development forest and agricultural biomass recycling is proposed, propulsion Biomass Industry is put forth effort on and is developed, Devoting Major Efforts To Developing new technology,
New product, makes the rising industry for promoting biomass resource efficiently to utilize.Therefore, oil-tea camellia husks high-grade resource profit is carried out
With, both it being beneficial to promote the sustainable development of China's camellia oleiferaindustry, can increase economic efficiency again.
At present, the research on oil-tea camellia husks is less both at home and abroad, and oil-tea camellia husks are mainly used in extraction Tea Saponin, wood
Sugar, furfural and prepare activated carbon etc..Using natural plant fibre filling prepare the research of biomass composite more into
It is ripe, but with oil-tea camellia husks, as prepared by raw material, whether biomass composite is feasible not to be mentioned yet at present.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to be mentioned and defect in background above technology, there is provided one
Plant the method for preparing biomass composite as raw material with oil-tea camellia husks, the biomass prepared using the method for the invention
Composite materials property is excellent, can reach the relevant criterion of wood plastic composite industry.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of biomass composite of oil-tea camellia husks base, the biomass composite include modified oil-tea camellia husks powder and
Polypropylene, the weight/mass percentage composition that the modified oil-tea camellia husks powder accounts for the biomass composite is 30%-70%.It is described to change
Property oil-tea camellia husks powder be by after oil-tea camellia husks powder elder generation through sodium hydroxide solution pretreatment, pulverizer is crushed, coupling agent solution is modified
Obtain.
A kind of method for preparing biomass composite as raw material with oil-tea camellia husks, comprises the following steps：
(1) oil-tea camellia husks are pre-processed using alkaline solution, after the completion of pretreatment, oil-tea camellia husks is cleaned in repeatedly
Property, after ventilation filters off moisture, the dry for standby under the conditions of 103 ± 2 DEG C；
(2) to the preprocessed oil-tea camellia husks for obtaining, selected removal of impurities place to go other debris, such as oil tea in addition to oil-tea camellia husks
After seed, branch, leaf etc., crushed with pulverizer, cross 40~100 mesh sieves, obtain oil-tea camellia husks powder；
(3) ethanol and coupling agent are mixed to get coupling agent solution, by the oil-tea camellia husks powder addition coupling agent solution
Treatment is modified, it is well mixed after shelving 12h~24h under cool environment；
(4) the oil-tea camellia husks powder that modified treatment is obtained is dried into more than 8h under the conditions of 103 ± 2 DEG C；Machine liter to be mixed
Temperature to 148 DEG C~176 DEG C, by oil-tea camellia husks powder and polypropylene in mix in kneading machine, to batch mixing color it is uniform, it is prepared to mix
Material A；
(5) after after batch mixing A coolings, batch mixing A is added into the granulation of comminutor block-by-block, mixed material B is obtained；
(6) it is mixed material B is evenly laid out in mould, be 150 DEG C~190 DEG C in hot pressing temperature, hot pressing pressure be 3MPa~
5MPa, after hot-forming 15min, cooling and demolding obtains the biomass composite.
It is 1 by solid-liquid mass ratio:10~1:20, it is preferred that solid-liquid mass ratio is 1：10, by alkaline solution and oil-tea camellia husks
Mixing 0.5h~3h, the alkaline solution is NaOH solution, and the concentration of the alkaline solution is 1%~2%.To setting time
Afterwards, oil-tea camellia husks are cleaned to neutrality repeatedly, in ventilation filter off moisture after in 103 ± 2 DEG C of baking ovens dry for standby.
Alkali lye eliminates the wax coat and grease on oil-tea camellia husks surface first, while also causing the SiO in shell2Formed
Nonpolar surface structure is destroyed, and the internal structure of fiber is showed to come, and the hydroxyl in three elements can connect with drop well
Touch, then improve the surface wettability of shell.During preparing wood-based plate, contact angle big I of the liquid to raw material surface
To reflect wetability of the adhesive to raw material to a certain extent, the presence of the nonpolar surface structure of oil-tea camellia husks can influence glue
The adhesion effect of stick, then causes that the timber intensity with oil-tea camellia husks preparation is undesirable, and after alkaline solution treatment, camellia oleifera fruit
The wetability of shell is improved, be conducive to improve artificial board mechanical strength, through inventor study find, alkaline solution it is dense
It is 1%~2% to spend, and solid-liquid mass ratio is 1:10~1:20, preferably 1：When 10, for the surface wettability for improving oil-tea camellia husks
Effect is best.When NaOH solution concentration is too low, it is impossible to fully dissolve grease, but because oil-tea camellia husks surface oil content is less,
And surface wax coat is cracked after drying, so when NaOH solution concentration is too high, cellulose, half of oil-tea camellia husks will be dissolved
Cellulose, lignin.
Further, in the step (3), coupling agent is the one kind in Silane coupling agent KH550, KH560, KH570, even
Connection agent can improve compatibility between inorganic filler, inorfil and matrix resin, at the same can also improve oil-tea camellia husks powder with
State of interface between polypropylene.Because main component is cellulose in oil-tea camellia husks, substantial amounts of hydroxyl is contained in cellulose, these
Hydroxyl formed intermolecular hydrogen bonding or intramolecular hydrogen bond, make oil-tea camellia husks powder that there is water imbibition, hydroscopicity up to 8%~12%, and
Polarity is very strong；And polypropylene is nonpolar, with hydrophobicity, so compatibility between the two is poor, the cohesive force at interface
Very little.Come modified polypropene and oil-tea camellia husks surface using appropriate coupling agent, can carry between oil-tea camellia husks powder and polypropylene
Interface affinity, and modified oil-tea camellia husks powder filler has enhanced property, can well transmit filler with poly- third
Stress between alkene, so as to reach the effect of enhancing composite material strength.The addition of the coupling agent be oil-tea camellia husks powder and
The 1%~5% of polypropylene quality summation, concentration of alcohol is 93%~96%.
Compared with prior art, the advantage of the invention is that：
The present invention use oil-tea camellia husks powder/PP composites, will often be dropped at present or burning disposal oil-tea camellia husks
Fully utilize, the composite that prepared performance can be suitable with Poplar Powder/PP composite properties.Can be sent out by the present invention
The advantages of waving inexpensive, renewable oil-tea camellia husks, abundance and concentrate, changes the wasting of resources in the past, the utilization of pollution environment
Approach, alleviates wooden resource disparities between supply and demand and environmental pollution increasingly serious problems could be made that significant contribution to China.
Specific embodiment
For the ease of understand the present invention, below in conjunction with explanation preferred embodiment to invent herein do more comprehensively, it is careful
Ground description, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limitation of the invention
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can be prepared by existing method.
Embodiment：
With reference to GB/T 17657-2013《Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels》Test all sheet materials
MOR, elastic modelling quantity and impact strength.
Embodiment 1
The biomass composite of the oil-tea camellia husks base of the present embodiment is included by oil-tea camellia husks powder and the polypropylene composite materials of being modified
Form, wherein, the weight/mass percentage composition that modified oil-tea camellia husks powder accounts for biomass composite is 40%.
The present embodiment includes in the method that oil-tea camellia husks prepare biomass composite as raw material：
(1) it is 1 by liquid-solid ratio:10, the NaOH solution that concentration is 1% is mixed with oil-tea camellia husks, in 20 DEG C of conditions, pre- place
The reason time is 1h, oil-tea camellia husks is cleaned repeatedly into neutrality, after ventilation filters off moisture, is dried in 103 DEG C of baking ovens standby
With；
(2) by the preprocessed oil-tea camellia husks for obtaining of step (1), after selected removal of impurities, 60 mesh are crossed after being crushed with pulverizer
~80 mesh sieves, obtain oil-tea camellia husks powder；
(3) coupling agent solution is configured with 95% ethanol, treatment is modified to oil-tea camellia husks powder, be well mixed after cool place
Shelve 24h under environment, coupling agent be KH550, the addition of the coupling agent is oil-tea camellia husks powder and polypropylene quality summation
3%；
(4) the oil-tea camellia husks powder that modified treatment is obtained is dried into more than 8h under the conditions of 103 DEG C；Machine to be mixed is warmed up to
150 DEG C, be 4 by oil-tea camellia husks powder and PP mass ratioes：6, it is equal to batch mixing color by oil-tea camellia husks powder with PP in mixing in kneading machine
Untill even, batch mixing A is obtained；
(5) after after batch mixing cooling, batch mixing is added into the granulation of comminutor block-by-block, mixed material B is obtained；
(6) it is mixed material B is evenly laid out in mould, it is 180 DEG C in hot pressing temperature, hot pressing pressure is 4MPa, hot-forming
After 15min, cooling and demolding obtains the biomass composite of oil-tea camellia husks base.
Use the oil-tea camellia husks prepared in the method that oil-tea camellia husks prepare biomass composite as raw material of the present embodiment
The mechanical property of powder/PP composites can reach the relevant criterion of wood plastic composite industry, impact strength and MOR
Suitable with the Poplar Powder/PP composites prepared under the same terms, specific performance test data is：Impact strength is 10.08/
KJ·m2, MOR is 37.81MPa, elastic modelling quantity 1930MPa.
Embodiment 2
The biomass composite of the oil-tea camellia husks base of the present embodiment is included by oil-tea camellia husks powder and the polypropylene composite materials of being modified
Form, wherein, the weight/mass percentage composition that modified oil-tea camellia husks powder accounts for biomass composite is 50%.
The present embodiment includes in the method that oil-tea camellia husks prepare biomass composite as raw material：
(1) it is 1 by liquid-solid ratio:10, the NaOH solution that concentration is 1% is mixed with oil-tea camellia husks, under the conditions of 20 DEG C, in advance
Process time is 1h, oil-tea camellia husks is cleaned repeatedly into neutrality, after ventilation filters off moisture, is dried in 103 DEG C of baking ovens
It is standby；
(2) by the preprocessed oil-tea camellia husks for obtaining of step (1), after selected removal of impurities, 40 mesh are crossed after being crushed with pulverizer
~60 mesh sieves, obtain oil-tea camellia husks powder；
(3) coupling agent solution is configured with 95% ethanol, treatment is modified to oil-tea camellia husks powder, be well mixed after cool place
Shelve 24h under environment, coupling agent be KH560, the addition of the coupling agent is oil-tea camellia husks powder and polypropylene quality summation
3%；
(4) the oil-tea camellia husks powder that modified treatment is obtained is dried into more than 8h under the conditions of 103 ± 2 DEG C；Machine liter to be mixed
Temperature, to 160 DEG C, is 5 by oil-tea camellia husks powder and PP mass ratioes：5, by oil-tea camellia husks powder and polypropylene (PP) in mixing in kneading machine,
To batch mixing color it is uniform, batch mixing A is obtained；
(5) after after batch mixing cooling, batch mixing is added into the granulation of comminutor block-by-block, mixed material B is obtained；
(6) it is mixed material B is evenly laid out in mould, it is 180 DEG C in hot pressing temperature, hot pressing pressure is 4MPa, hot-forming
After 15min, cooling and demolding obtains the biomass composite of oil-tea camellia husks base.
Use the oil-tea camellia husks prepared in the method that oil-tea camellia husks prepare biomass composite as raw material of the present embodiment
The mechanical property of powder/PP composites can reach the relevant criterion of wood plastic composite industry, and specific performance test data is：
Impact strength is 8.35/KJm2, MOR is 35.67MPa, elastic modelling quantity 1990MPa.
Embodiment 3
The biomass composite of the oil-tea camellia husks base of the present embodiment is included by oil-tea camellia husks powder and the polypropylene composite materials of being modified
Form, wherein, the weight/mass percentage composition that modified oil-tea camellia husks powder accounts for biomass composite is 70%.
The present embodiment includes in the method that oil-tea camellia husks prepare biomass composite as raw material：
(1) it is 1 by liquid-solid ratio:10, the NaOH solution that concentration is 1% is mixed with oil-tea camellia husks, under the conditions of 20 DEG C, in advance
Process time is 1h, oil-tea camellia husks is cleaned repeatedly into neutrality, after ventilation filters off moisture, is dried in 103 DEG C of baking ovens
It is standby；
(2) by the preprocessed oil-tea camellia husks for obtaining of step (1), after selected removal of impurities, 80 mesh are crossed after being crushed with pulverizer
~100 mesh sieves, obtain oil-tea camellia husks powder；
(3) coupling agent solution is configured with 95% ethanol, treatment is modified to oil-tea camellia husks powder, be well mixed after cool place
Shelve 24h under environment, coupling agent be KH570, the addition of the coupling agent is oil-tea camellia husks powder and polypropylene quality summation
3%；
(4) the oil-tea camellia husks powder that modified treatment is obtained is dried into more than 8h under the conditions of 103 ± 2 DEG C；Machine liter to be mixed
Temperature, to 160 DEG C, is 7 by oil-tea camellia husks powder and PP mass ratioes：3, by oil-tea camellia husks powder and polypropylene (PP) in mixing in kneading machine,
To batch mixing color it is uniform, batch mixing A is obtained；
(5) after after batch mixing cooling, batch mixing is added into the granulation of comminutor block-by-block, mixed material B is obtained；
(6) it is mixed material B is evenly laid out in mould, it is 180 DEG C in hot pressing temperature, hot pressing pressure is 4MPa, hot-forming
After 15min, cooling and demolding obtains the biomass composite of oil-tea camellia husks base.
Use the oil-tea camellia husks prepared in the method that oil-tea camellia husks prepare biomass composite as raw material of the present embodiment
The mechanical property of powder/PP composites can reach the relevant criterion of wood plastic composite industry, and specific performance test data is：
Impact strength is 8.05/KJm2, MOR is 26.02MPa, elastic modelling quantity 2024MPa.
Claims (8)
1. a kind of biomass composite of oil-tea camellia husks base, it is characterised in that the biomass composite includes modified oil
Tea fruit shell powder and polypropylene, the weight/mass percentage composition that the modified oil-tea camellia husks powder accounts for the biomass composite are 30%-
70%.
2. the biomass composite of oil-tea camellia husks base according to claim 1, it is characterised in that the modified oil-tea camellia husks
Powder is modified and obtained through sodium hydroxide solution pretreatment, pulverizer crushing, coupling agent solution by after oil-tea camellia husks powder elder generation.
3. a kind of method for preparing biomass composite as raw material with oil-tea camellia husks, it is characterised in that comprise the following steps：
(1) oil-tea camellia husks are pre-processed using sodium hydroxide solution, after the completion of pretreatment, oil-tea camellia husks are cleaned to neutrality repeatedly,
After ventilation filters off moisture, the dry for standby under the conditions of 103 ± 2 DEG C；
(2) to the preprocessed oil-tea camellia husks for obtaining, after selected removal of impurities, crushed with pulverizer, obtain oil-tea camellia husks powder；
(3) coupling agent solution is mixed to get with ethanol and coupling agent, is carried out during oil-tea camellia husks powder is added into the coupling agent solution
Modification, it is well mixed after shelving 12~24h under cool environment；
(4) the oil-tea camellia husks powder that modified treatment is obtained is dried into more than 8h under the conditions of 103 ± 2 DEG C；Machine to be mixed is warming up to
148 DEG C~176 DEG C, by the oil-tea camellia husks powder and polypropylene in mixing in kneading machine, to batch mixing color it is uniform, be obtained mixed
Material A；
(5) after after batch mixing A coolings, batch mixing A is added into the granulation of comminutor block-by-block, mixed material B is obtained；
(6) it is mixed material B is evenly laid out in mould, it is 170 DEG C~190 DEG C in hot pressing temperature, hot pressing pressure is 3Mpa~5MPa
Under the conditions of, hot pressing 15min, cooling and demolding obtains the biomass composite.
4. the method for preparing biomass composite as raw material with oil-tea camellia husks according to claim 3, it is characterised in that institute
State in step (1), the method for pretreatment is：It is 1 by solid-liquid mass ratio:10~1:20, by sodium hydroxide solution and oil-tea camellia husks
Mixing 0.5h~3h.
5. the method for preparing biomass composite as raw material with oil-tea camellia husks according to claim 4, it is characterised in that institute
State in step (1), the concentration of the sodium hydroxide solution is 1%~2%.
6. the method for preparing biomass composite as raw material with oil-tea camellia husks according to claim 3, it is characterised in that institute
State in step (2), cross 40~100 mesh sieves, obtain oil-tea camellia husks powder.
7. the method for preparing biomass composite as raw material with oil-tea camellia husks according to claim 3, it is characterised in that institute
State in step (3), coupling agent is the one kind in Silane coupling agent KH550, KH560, KH570.
8. the method for preparing biomass composite as raw material with oil-tea camellia husks according to claim 4, it is characterised in that institute
The addition for stating coupling agent is the 1%~5% of oil-tea camellia husks powder and polypropylene quality summation.
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| CN201710124133.3A CN106832591A (en) | 2017-03-03 | 2017-03-03 | A kind of biomass composite of oil-tea camellia husks base and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694526A (en) * | 2017-09-30 | 2018-02-16 | 福建省林业科学研究院 | Adsorbent prepared by a kind of oil-tea camellia husks extract and preparation method thereof |
| CN113105681A (en) * | 2021-03-08 | 2021-07-13 | 华南农业大学 | Camellia oleifera shell-based biomass composite material and extrusion molding method thereof |
| CN115433409A (en) * | 2022-09-30 | 2022-12-06 | 武汉轻工大学 | Preparation method of camellia oleifera shell-based biomass composite material and polyethylene wood-plastic decorative plate |
| CN116515129A (en) * | 2023-06-12 | 2023-08-01 | 华南农业大学 | Coating modification method of camellia oleifera shells and application thereof |
-
2017
- 2017-03-03 CN CN201710124133.3A patent/CN106832591A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 彭开元: "油茶果壳基木质复合材料的制备与性能研究", 《中国优秀硕士学位论文全文数据库，工程科技第Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694526A (en) * | 2017-09-30 | 2018-02-16 | 福建省林业科学研究院 | Adsorbent prepared by a kind of oil-tea camellia husks extract and preparation method thereof |
| CN113105681A (en) * | 2021-03-08 | 2021-07-13 | 华南农业大学 | Camellia oleifera shell-based biomass composite material and extrusion molding method thereof |
| CN115433409A (en) * | 2022-09-30 | 2022-12-06 | 武汉轻工大学 | Preparation method of camellia oleifera shell-based biomass composite material and polyethylene wood-plastic decorative plate |
| CN116515129A (en) * | 2023-06-12 | 2023-08-01 | 华南农业大学 | Coating modification method of camellia oleifera shells and application thereof |
| CN116515129B (en) * | 2023-06-12 | 2024-02-09 | 华南农业大学 | Coating modification method of camellia oleifera shells and application thereof |
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Application publication date: 20170613 |