CN102212259B - Starch and polycaprolactone blend and preparation method and application thereof - Google Patents

Starch and polycaprolactone blend and preparation method and application thereof Download PDF

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Publication number
CN102212259B
CN102212259B CN2011101135873A CN201110113587A CN102212259B CN 102212259 B CN102212259 B CN 102212259B CN 2011101135873 A CN2011101135873 A CN 2011101135873A CN 201110113587 A CN201110113587 A CN 201110113587A CN 102212259 B CN102212259 B CN 102212259B
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starch
blend
water
polycaprolactone
carbon source
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CN102212259A (en
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吴为中
吴官清
朱擎
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Peking University
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Peking University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention discloses a starch and polycaprolactone blend, a preparation method thereof and application of the blend used as a solid carbon source to the removal of nitrate from water. The preparation method comprises the following steps of: adding additives such as a plasticizer and the like into starch and polycaprolactone which are taken as raw materials, stirring and mixing uniformly, performing one-time extrusion by using a twin-screw extruder, and pelleting to obtain a product. The starch/polycaprolactone blend can be synchronously taken as a denitrification carbon source and a biofilm carrier in water treatment, so that the disadvantages of the use of the conventional liquid denitrification carbon source are overcome; moreover, the cheap starch is added into the blend, so the method has a remarkable economic advantage compared with a method in which the polycaprolactone is used as the solid carbon source. The blend can be applied to biological denitrification fields of surface water containing nitrates which exceed the standard, underground water, advanced treatment of sewage treatment plants and the like.

Description

Starch and polycaprolactone blend and its production and application
Technical field
The invention belongs to environmental technology field, be specifically related to the preparation method of a kind of starch and polycaprolactone blend and as the application of solid carbon source nitrate in removing water.
Background technology
The nitrate pollution problem of low organically-polluted water is the outstanding problem that China finishes point source pollution control FUTURE ENVIRONMENT pollution afterwards.Along with the operational management that strictness implements to cut dirty control source, enhanced sewage treatment plant, be the water pollution problems of discharge characteristics with occurring with low organic contamination, higher nitrogen.Reach the ecological water supplement of the water outlet of one-level A standard as sewage work, derive from confluxing of rainwash in rainy season face source, city etc. as water surrounding.If this class low-pollution water directly confluxes into lake, reservoir without further processing, cause exceeding standard and to become the subject matter of China's surface water environmental pollution based on the total nitrogen of nitrate nitrogen.
The removal of nitrate nitrogen is a bottleneck problem of water pollution control always.The nitrate how simply to remove efficiently in the water body is a global problem.The solid phase denitrification is the cutting edge technology of effectively preventing and treating the water surrounding pollution of nitrate nitrogen, is a kind of novel heterotrophic denitrification technology.It utilizes the water insoluble solid material to hang down the denitrification denitrogenation of organically-polluted water, different with traditional heterotrophic denitrification is, with the adhere to carrier of solid organic matters as microorganism, simultaneously again can be under the effect of microbial enzyme biodegrade, for denitrification provides carbon source.
At present, the solid carbon source that is used for denitrification denitrogenation mainly contains following 3 classes: the material of (1) rich cellulose, as cotton (Volokita et al, 1996a; Jin Zanfang etc., 2006), straw (Aslan and Turkman, 2005; Soares and Abeliovich, 1998), reed natural phant such as (Ovez, 2006), and broken newspaper (Volokita et al, 1996b) etc.; (2) bacterium synthetic polymkeric substance mainly refers to polyhydroxyalkanoate (PHAs) class material (Hiraishi and Khan, 2003); (3) polymkeric substance of synthetic is as poly(lactic acid) (PLA), polycaprolactone (PCL) (Hiraishi and Khan, 2003; Boley et al, 2000).
Utilize the natural plant composition of rich cellulose to carry out the solid phase denitrification and can significantly reduce running cost, and when guaranteeing certain hydraulic detention time and regularly adding new carbon source, can effectively remove the nitrate in the water.But because crude substance all contains certain water-soluble nutritive ingredient, so the DOC in the initial operating stage water outlet, colourity, total plate count etc. are generally higher, effluent quality is relatively poor, so also need subsequent disposal such as sand filtration or charcoal absorption.In addition, hemicellulose in the lignocellulose material and lignin component not readily biodegradable, particularly xylogen are to be difficult to by biodegradable, so may there be the problem of xylogen accumulation in reactor when moving continuously.The polymkeric substance of bacterium and synthetic is fast as the denitrification process denitrification rate of solid carbon source, efficient is high, and DOC content is low in the water outlet, and pH changes little, and is little to the influence of effluent quality.But compare its denitrification cost with the natural phant of rich cellulose much bigger, also do not possess economic serviceability at present.For this reason, developing the solid carbon source that possesses technology and economic feasibility has become and has limited this technology popularization key in application.
Starch not only has fabulous biodegradability, but also is cheap natural reproducible resource, has been subjected to paying close attention to widely for this reason.Cost be can effectively reduce after starch or treated starch and the degradable polymer blend, polyvinyl alcohol (PVA), poly-light basic butyric fat (PHB), poly-hydroxypentanoic acid fat (PHV), PHB-PHV multipolymer, polycaprolactone (PCL) etc. are mainly with the degradable synthetic materials of starch blending.The research of at present existing many starch and PCL blend, but its purpose all mainly concentrates on the performance of raising blended product as degradable plastics, as the tensile property of blend." Mater-Bi Z " as Novomont company is that thermoplastic starch and PCL are the blend of main component, is to be used for blown film and film-making.
Summary of the invention
One of purpose of the present invention has provided starch and polycaprolactone blend and preparation method thereof.
Two of purpose of the present invention is to hang down the denitrogenation of C/N than azotate pollution water with the starch of preparation and polycaprolactone blend as the carrier that the carbon source and the microbial film of biological denitrification adheres to.
The component of starch provided by the invention and polycaprolactone blend (mass parts) comprising: 20～65 parts of starch, 25～70 parts of polycaprolactones, 10～20 parts of water, 0～10 part of wood powder and 0～2 part of silane coupling agent.Its preparation method is after above-mentioned materials is stirred, to get final product in 130～170 ℃ of extruding pelletizations in twin screw extruder.
Used starch is one or more the mixing in W-Gum, potato starch, the tapioca (flour) in the aforesaid method.
The molecular weight of used polycaprolactone is 40000～100000 in the aforesaid method.
The particle diameter of used wood powder is between 200～400 orders in the aforesaid method.
Used silane coupling agent is one or more the mixing among KH-550, KH-560 and the KH-570 in the aforesaid method.
Starch provided by the invention and polycaprolactone blend can have been realized effective denitrogenation of the low C/N water of azotate pollution simultaneously as denitrifying carbon source and biofilm carrier.Starch/PCL blend is as the denitrification solid carbon source, its special emphasis in the preparation with have as degradable plastics significantly different.Do not need higher tensile property during as solid carbon source, but material must hang down leaching, all components is biological degradation completely etc. all.
The present invention has the following advantages:
1, owing to added cheap reproducible starch among the present invention in PCL, feasible denitrogenation cost with this blend reduces greatly.
2,, avoided the process of elder generation, thereby not only simplified production technique but also reduced production cost the starch thermoplastification because the present invention is being a disposable extruding pelletization in the forcing machine.
3, adopt the blend of the present invention's preparation as the denitrification solid carbon source time, have start time short, denitrification rate is fast and the variation of envrionment conditions is had the characteristics of very strong adaptive faculty, and all components all can be degraded fully, can not bring secondary pollution to environment.
4, the blend that adopts the present invention to prepare can be used for the denitrogenation processing of low C/N surface water, underground water and effluent of municipal sewage plant as the denitrification solid carbon source time.
5, adopt the blend of the present invention's preparation not only to serve as the required carbon source of denitrification but also as biomembranous carrier, overcome tradition and use the uppity shortcoming of carbon source dosage in the liquid carbon source biological denitrification process, avoided carbon source to add the excessive risk that causes secondary pollution, this is further raising and innovation to traditional technology.
Embodiment
Provide embodiment below so that the present invention is described further; be pointed out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area foregoing according to the present invention still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes.
The preparation method of starch/polycaprolactone blend:
Embodiment 1
After 55 parts of W-Gums, 30 parts of polycaprolactones (molecular weight 60000), 14 parts of water and 1 part of KH-550 silane coupling agent stirred, in twin screw extruder in 130～170 ℃ of extruding pelletizations.
Embodiment 2
After 40 parts of W-Gums, 40 parts of polycaprolactones (molecular weight 40000), 15 parts of water, 3 parts of wood powders and 2 parts of KH-560 silane coupling agents are stirred, in twin screw extruder in 130～170 ℃ of extruding pelletizations.
Embodiment 3
After 30 portions of tapioca (flour)s, 50 parts of polycaprolactones (molecular weight 80000), 15 parts of water and 5 parts of wood powders are stirred, in twin screw extruder in 130～170 ℃ of extruding pelletizations.
The denitrification of starch/polycaprolactone blend is used:
1, the biofilm of denitrifying microorganism.Reactor is the packed bed pattern, and the blend particle (particle diameter 0.4cm) for preparing is filled in the reactor, and packing height is 2/3rds of a reactor, the upflowing water inlet.In containing the former water of nitrate, add the active sludge of sewage disposal plant aeration tank, denitrifying microorganism is tamed.After treating the denitrification effect stability, domestication finishes.
2, denitrification denitrogenation.After domestication finishes, the normal operation of beginning reactor.The optimum temps of domestication and operation is 25～30 ℃.The former water that contains nitrate enters packed bed reactor from water tank by volume pump, and regulates the flow velocity of water by volume pump, guarantees certain hydraulic detention time.Under the effect of the denitrifying microorganism in packed bed of the nitrate nitrogen in the former water, progressively be reduced to nitrogen, discharged by venting port.
Application examples 1
The reactor specification is: 30cm * 150cm.In packed bed reactor, add starch/polycaprolactone blend of embodiment 1 as carbon source and biofilm carrier.Processed former water is the tap water of Kunming, adds NaNO 3Regulate NO 3-N concentration is 50mg/L, carries out denitrogenation processing under the following conditions:
Hydraulic detention time: 2 hours
Temperature: 30 ℃
pH：7.5
Former water DO:5.4mg/L
It is as shown in the table to handle back water quality:
Application examples 2
The reactor specification is: 30cm * 150cm.In packed bed reactor, add starch/polycaprolactone blend of embodiment 2 as carbon source and biofilm carrier.Processed former water is the tap water of Kunming, adds NaNO 3Regulate NO 3-N concentration is 30mg/L, carries out denitrogenation processing under the following conditions:
Hydraulic detention time: 1.5 hours
Temperature: 25 ℃
pH：7.5
Former water DO:4.5mg/L
It is as shown in the table to handle back water quality:
Figure BDA0000059072150000051

Claims (6)

1. starch and polycaprolactone blend is characterized in that as the purposes of denitrifying carbon source and biofilm carrier described starch and polycaprolactone blend are made up of following component (mass percent):
20～65% starch; 25～70% polycaprolactones; 10～20% water; 0～10% wood powder and 0～2% silane coupling agent.
2. purposes as claimed in claim 1 is characterized in that, described starch is one or more the mixing in W-Gum, potato starch, the tapioca (flour).
3. purposes as claimed in claim 1 is characterized in that, the molecular weight of described polycaprolactone is 40000～100000.
4. purposes as claimed in claim 1 is characterized in that, the particle diameter of described wood powder is between 200～400 orders.
5. purposes as claimed in claim 1 is characterized in that, described silane coupling agent is one or more the mixing among KH-550, KH-560 and the KH-570.
6. as purposes as described in arbitrary among the claim 1-5, it is characterized in that described denitrifying carbon source and biofilm carrier are applied to remove nitrate in the water.
CN2011101135873A 2011-05-04 2011-05-04 Starch and polycaprolactone blend and preparation method and application thereof Expired - Fee Related CN102212259B (en)

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WO2014046321A1 (en) * 2012-09-21 2014-03-27 (주)엘지하우시스 Biodegradable panel
CN105600926A (en) * 2016-03-21 2016-05-25 卓勒（上海）环境工程有限公司 Bio-degradable sustained-release carbon material and preparation method thereof
CN106986450A (en) * 2017-05-08 2017-07-28 宁波市川宁环保科技有限公司 A kind of denitrification organisms filler
CN107936504A (en) * 2017-11-17 2018-04-20 北京大学 Blend comprising PHBV and rice husk and its preparation method and application
CN107915969A (en) * 2017-11-17 2018-04-17 北京大学 Blend comprising starch, polylactic acid and rice husk and its preparation method and application
CN108793428A (en) * 2018-06-27 2018-11-13 郑州大学 A kind of preparation method of composite slow release carbon source
CN110407334B (en) * 2019-07-30 2021-09-28 南京大学 Preparation and application of synchronous denitrification biological filler for adsorbing nitrate ions
CN110668561B (en) * 2019-10-31 2021-03-16 同济大学 Organic composite powder carrier and application thereof in enhanced biological denitrification of town sewage treatment
CN110902821A (en) * 2019-12-09 2020-03-24 宁波首创厨余垃圾处理有限公司 Solid carbon source suitable for denitrification of high-concentration nitrate-nitrogen sewage and preparation method thereof
WO2021253144A1 (en) * 2020-06-15 2021-12-23 温州蓝宝科技有限公司 Novel solid carbon source and preparation method therefor
CN114291892A (en) * 2021-12-22 2022-04-08 重庆大学 Solid carbon source for denitrification of sewage with low carbon-nitrogen ratio and preparation method thereof
CN115259371A (en) * 2022-08-24 2022-11-01 温州市工业科学研究院 Pretreatment method of mushroom bran for preparing carbon source

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