WO2016015508A1

WO2016015508A1 - Straw biomass modification and method of use

Info

Publication number: WO2016015508A1
Application number: PCT/CN2015/078742
Authority: WO
Inventors: 陈集双; 张文涛; 蒋海侠; 陈锦周; 邓归阁; 王耀东; 金磊磊
Original assignee: 南京工业大学
Priority date: 2014-07-31
Filing date: 2015-05-12
Publication date: 2016-02-04
Also published as: CN105315688A

Abstract

A composite material derived from straw, that is, a modified plastic straw biomass obtained by modifying straw powder with mineral powder and auxiliary, and a method of further combining the modified straw biomass and plastic to form new materials and manufacturing straw-plastic products using same; the method comprises: grinding the straw biomass to a specific fineness, mixing with mineral powder under the action of esterifying and coupling agents to form modified straw powder, combining the straw powder with plastic under the action of additives such as a grafting agent to form materials and products as alternatives to wood-plastics and plastics.

Description

Method for modifying straw biomass and using method thereof

Technical field

The invention belongs to the field of agriculture and plastic industry, and particularly relates to a straw-derived composite material, that is, the use of ore powder and an auxiliary agent to modify the straw powder to obtain a plastic modified straw powder, and further to modify the straw powder and the plastic. New materials and straw plastic products formed by compounding.

Background technique

The stock of straw biomass is huge, both waste and resources, and thus has broad application potential. However, whether using straw for biogas or processing pulp, it will bring waste liquid waste, resulting in “waste and waste”. The full-price utilization of straw biomass or the use of waste residue (ash) in the processing of straw is of great significance. The replacement of lignocellulose by straw biomass to prepare straw-plastic products is one of the ways to solve the above problems.

In view of the fact that the composite of plant fiber material and plastic can realize the full-price utilization of straw and has environmentally friendly properties, the application that has been obtained can also explain the feasibility and practical value of the present invention. For example, the patent application with the application number of 200410021704.3 prepares a modified plastic with 100 parts of high-pressure polyethylene with a ratio of 10-60 parts of calcium powder, and has the characteristics of abrasion resistance, impact resistance and anti-aging, but the patent does not add straw powder. The patent application with the application number of 200610030671.8 directly forms a product by melt-stirring the ultrafine wood powder, the ultrafine ore powder and the waste plastic, but the patent does not form the modified straw powder material, but directly produces the finished product. The patent application with the application number 201310029919.9 is injected into the wood powder with the montmorillonite suspension to enhance the interfacial compatibility of the wood-plastic composite material and improve the use efficiency of the wood powder, but the wood plastic product needs to be dried during the production process. Obviously, it does not match the plasticity characteristics pursued by straw plastic materials.

The main problems faced by the full-price development of straw-plastic materials instead of wood-plastic materials are: First, the straw has a porous structure, the total bulk density is about 0.4, and the total bulk density of the plastic is about 1.0; second, the ultrastructure of straw The complexity appears, especially the presence of hydrophilic groups affects the plasticity of straw biomass. For the above reasons, the straw powder is easily separated from the plastic base material and agglomerated when mixed with the plastic base material, causing the destruction of the ordered structure inside the plastic, and possibly reducing the strength of the composite material.

Summary of the invention

In view of the above situation, after long-term exploration, the inventors chose straw as the material, and used the ore powder with a total bulk density of about 2.0 to increase the quality of the straw powder. At the same time, the ester powder and the coupling agent were used to feed the straw powder. The line is modified to obtain a modified straw powder. The invention also aims at the characteristics of the modified straw powder, and studies the characteristics of the new straw material and the product by using the modified straw powder, and strengthens the strength and stability of the straw plastic by adding corresponding additives.

Specifically, the present invention adopts the following technical solutions:

A method for modifying straw biomass, characterized in that the method comprises the following steps:

a) crushing the straw to 70-800 mesh, and drying to a moisture content of 1.5-31%;

b) first heat the straw powder, heat it to 70-150 ° C, and keep it for more than 10 minutes, then add mineral-based raw materials, high-speed mixing under negative pressure, adding esterification agent and coupling agent in sequence , wherein the amount of the mineral-based raw material is 90-300 parts, the amount of the esterifying agent is 0.5-25 parts, and the amount of the coupling agent is 0-5.5 parts.

c) After the components are thoroughly mixed, the mixture is kept and maintained at a temperature of 80-180 ° C for more than 10 minutes to obtain a modified straw powder.

In a preferred case, the straw in step a) is comminuted to 80-250 mesh, the moisture content is 4-10%; the straw powder in step b) is heated to 80-120 ° C; the temperature in step c) is 110- 130 ° C.

Preferably, the mineral-based raw material refers to a quartz powder, a mica powder calcium carbonate, a talc powder, a calcium carbonate, a wollastonite, a calcium silicate, a glass microbead, an aluminum sulfate, a fly ash, or the like, or a divalent or trivalent mineral raw material. Or a mixture of ores; the esterifying agent means maleic anhydride, acetic acid, caprolactam, phthalic anhydride, succinic anhydride, acrylic acid, polymethacrylic acid, polyisobutylene, ethylene propylene ternary rubber or one or more of the above The compounding agent of a plurality of esterifying agents means a commercial silane coupling agent, an isocyanate coupling agent, a titanate coupling agent or a combination of one or more coupling agents described above.

Preferably, the mineral-based raw material refers to a powder pulverized by the above-mentioned commercial ore raw material, having a particle size of 80-3000 mesh and drying to a moisture content of 1.5-31%.

More preferably, the mineral-based raw material has a particle size of preferably from 120 to 1600 mesh and a moisture content of from 4 to 12%.

The invention also discloses a modified straw biomass material prepared according to the above modification method.

The invention further discloses a method for using the modified straw biomass material, characterized in that the modified straw biomass material and the plastic masterbatch are plasticized and combined under the condition of adding a grafting agent and a plasticizer. The straw plastic masterbatch, wherein the modified straw biomass is 100 parts, the amount of the plastic masterbatch is 99-550 parts, the amount of the grafting agent is 1.0-5.5 parts, and the amount of the plasticizer is 0.5-5.5 parts.

Preferably, the grafting agent is diethylamine-dimethyl sulfoxide, paraformaldehyde or a raw material having similar functions, or a combination of several kinds of the foregoing grafting agents; the plasticizer refers to phthalic acid Dioctyl or dibutyl or a combination of one or more of the foregoing plasticizers; plastic masterbatch including polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC) , polylactic acid (PLA), polyamide (PA), polyoxymethylene (POM), polystyrene (PS), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polymethyl methacrylate (PMMA) A combination of one or at least two of polyphenylene ether (PPO) or acrylonitrile-styrene-butadiene copolymer (ABS), or recycled plastic waste.

Preferably, the modified straw biomass material and the plastic masterbatch are directly processed into straw plastic rattan to replace the whole plastic rattan, wherein the modified straw biomass is 100 parts, and the plastic masterbatch is used in an amount of 100 - 550 parts, in addition, the straw plastic rattan is processed into a flat or round shape, which is woven from single or multiple strands.

More preferably, the straw plastic rattan is woven from 1 to 3 strands.

Advantageous Effects: The modified straw biomass material manufactured by the method of the present invention can be used in the wood plastic industry instead of wood powder to form a new straw plastic material; not only find new uses for farm straw, but also reduce the use of wood, and Environmentally friendly.

detailed description

The invention discloses a method for modifying straw, which can improve the bulk density of the straw powder by modifying the straw to realize the compounding of the straw powder and the plastic material, thereby obtaining the composite material of the straw source, that is, the composite material of the straw and the ore powder. The invention also discloses a method for manufacturing straw modified composite plastic by compounding the modified straw powder with plastic, that is, by further compounding the modified straw powder with plastic to form a new straw-plastic material, so-called straw Plastic or straw plastic.

The invention firstly pulverizes the straw biomass to a certain fineness, and mixes with the ore powder which is smaller than the straw biomass to form a modified straw powder, and the latter is further compounded with plastic to form a new substitute for wood plastic and substitute plastic. New materials and new products.

The method for modifying the straw powder of the present invention utilizes the property of the mineral powder to modify the straw powder to be able to be composited with plastic. The straw powder refers to the ash and other bio-based minerals formed during the processing of the straw by the pulverization process to obtain the full-price straw powder or straw; the straw includes farmland straw, especially rice, wheat, corn, sorghum, barley, etc. Straws of gramineous plants and cotton, rapeseed and other crops, including straws of invasive plant rice grass, also include fiber-containing waste in food processing, especially peanut shell and ginkgo leaf extract residue.

The technical solutions of the present invention will be further described with reference to the specific embodiments, but the scope of the present invention is not limited.

Example 1:

Straw straw is selected, crushed to 80 mesh by mechanical equipment, and dried to a water content of 4%; in a high-mixer, 48 parts of the above-mentioned treated straw straw powder is added, heated and dried, and heated to 90 ° C, rotating speed 360-410 r /min, keep 10min; add 48 parts of commercial quartz powder, 300 mesh, water content is 6%; open negative pressure function, relative vacuum degree reaches -0.096MPa, temperature is 115 °C, speed is 420~560r/min, start mixing . In the mixing process, 3 parts of caprolactam and 1 part of silane coupling agent were sequentially added and mixed for 20 minutes to obtain modified straw straw powder. The moisture absorption rate of the modified straw powder was 16.53%, and the moisture absorption rate of the unmodified straw straw powder was 22.45%, and the hygroscopicity decreased.

Example 2:

The wheat straw was pulverized to 250 mesh and dried to a moisture content of 10%; the commercial calcium carbonate powder was 1600 mesh, and the moisture content was 12%; and the wheat straw powder was used as 100 parts, and the calcium carbonate powder was used in an amount of 300 parts. The wheat straw powder is first heated and dried in a high-mixer, heated to 110 ° C, and kept for 10 min, then the above commercial calcium carbonate powder is added, and high-speed mixing is carried out under a negative pressure state, and maleic anhydride is added during the mixing. And 2.5 parts each of the isocyanate coupling agent, heated to 130 ° C; mixed for 15 min, the modified wheat straw powder was obtained. The moisture absorption rate of the modified straw powder was 16.89%, and the moisture absorption rate of the unmodified wheat straw powder was 23.02%, and the hygroscopicity decreased.

Example 3:

Add 40 parts of modified straw powder in Practice 1 and 57 parts of polyethylene to a plastic internal mixer at a speed of 2490 rpm. Add 1.5 parts of paraformaldehyde and 1.5 parts of dioctyl phthalate in the mixing process. 15 min; the above treated mixture was blended and melted through a twin-screw extruder, and the extrusion process was carried out at 140 ° C to 210 ° C, and the extruded mixture was chopped to a 4-6 mm straw plastic master batch, and dried. To the water content of 4-7%, that is, the straw-plastic composite masterbatch. The modified straw powder obtained is combined with polyethylene to make a modified plastic masterbatch, and the straw plastic dinner plate is successfully prepared, which can be reused more than 6 times.

Example 4:

30 parts of the modified straw powder of the second embodiment and 65 parts of the raw material polyethylene were combined with the partial method of the second embodiment, and directly processed into straw plastic rattan, and the straw plastic rattan was a single-stranded circular shape.

Example 5:

Collecting the straw ash formed during the physical pulp of rice straw, pulverizing to 90 mesh, drying to 5% water content, adding 120 parts of polycarbonate, 1.5 parts of caprolactam, 2 parts of paraformaldehyde according to 100 parts of straw ash, in extrusion The modified straw plastic raw material is obtained in the equipment; the raw material can directly produce the straw plastic composite floor, and the prepared straw plastic composite floor has the characteristics of wear resistance and impact resistance.

The embodiments of the present invention have been described in detail above with reference to specific examples, but the present invention is not limited to the above embodiments, and can be made without departing from the scope of the present invention within the knowledge of those skilled in the art. Various changes.

Claims

A method for modifying straw biomass, characterized in that the method comprises the following steps:

a) crushing the straw to 70-800 mesh, and drying to a moisture content of 1.5-31%;

b) first heat the straw powder, heat it to 70-150 ° C, and keep it for more than 10 minutes, then add mineral-based raw materials, high-speed mixing under negative pressure, adding esterification agent and coupling agent in sequence , wherein the amount of the mineral-based raw material is 90-300 parts, the amount of the esterifying agent is 0.5-25 parts, and the amount of the coupling agent is 0-5.5 parts.

c) After the components are thoroughly mixed, the mixture is kept and maintained at a temperature of 80-180 ° C for more than 10 minutes to obtain a modified straw powder.
The method for modifying straw biomass according to claim 1, wherein in step a), the straw is pulverized to 80-250 mesh, and the moisture content is 4-10%; in step b), the straw powder is heated to 80. -120 ° C; maintaining temperature in step c) is 110-130 ° C.
The method for modifying straw biomass according to claim 1, wherein the mineral-based raw material refers to quartz powder, mica powder calcium carbonate, talc powder, calcium carbonate, wollastonite, calcium silicate, glass micro. a divalent or trivalent mineral raw material such as beads, aluminum sulfate, fly ash or a mixture of a plurality of ores; the esterifying agent means maleic anhydride, acetic acid, caprolactam, phthalic anhydride, succinic anhydride, acrylic acid, poly a combination of methacrylic acid, polyisobutylene, ethylene propylene ternary rubber or one or more esterifying agents described above; the coupling agent means a commercial silane coupling agent, an isocyanate coupling agent, a titanate coupling agent or Recombination of one or more of the above coupling agents.
The method for modifying straw biomass according to claim 1, wherein the mineral-based raw material refers to a powder pulverized by the commercial ore raw material, having a particle size of 80-3000 mesh, and drying to a moisture content. 1.5-31%.
The method for modifying straw biomass according to claim 4, wherein the mineral-based raw material has a particle size of preferably from 120 to 1600 mesh and a moisture content of from 4 to 12%.
A modified straw biomass material, characterized in that the modified straw biomass material is produced by the method according to any one of claims 1 to 5.
A method for using a modified straw biomass material according to claim 6, wherein the modified straw biomass material and the plastic masterbatch are plasticized and compounded in the case of adding a grafting agent and a plasticizer. Forming a straw plastic masterbatch, wherein the amount of the plastic masterbatch is 99-550 parts, the amount of the grafting agent is 1.0-5.5 parts, and the amount of the plasticizer is 0.5-5.5 parts, based on 100 parts of the modified straw biomass. .
The method for using a modified straw biomass material according to claim 7, wherein the grafting agent is diethylamine-dimethyl sulfoxide, paraformaldehyde or a raw material having similar functions, or a number The compounding agent of the foregoing grafting agent; the plasticizer refers to a combination of dioctyl phthalate, dibutyl ester or one or more of the aforementioned plasticizers; the plastic master batch comprises polyethylene (PE), poly Propylene (PP), polyvinyl chloride (PVC), polycarbonate (PC), polylactic acid (PLA), polyamide (PA), polyoxymethylene (POM), polystyrene (PS), polytetrafluoroethylene (PTFE) , one or at least two of polyphenylene sulfide (PPS), polymethyl methacrylate (PMMA), polyphenylene ether (PPO) or acrylonitrile-styrene-butadiene copolymer (ABS) Combination, or recycled plastic waste.
A method for using a modified straw biomass material according to claim 6, wherein the modified straw biomass material and the plastic masterbatch are directly processed into a straw plastic rattan to replace the whole plastic rattan strip. The amount of the plastic masterbatch is 100-350 parts, and the straw plastic rattan is processed into a flat shape or a round shape, and is woven by single or multiple strands.
The method of using a modified straw biomass material according to claim 9, wherein the straw plastic rattan is woven from 1 to 3 strands.