CN103145873B - Chitin deacetylation method - Google Patents
Chitin deacetylation method Download PDFInfo
- Publication number
- CN103145873B CN103145873B CN201110401667.9A CN201110401667A CN103145873B CN 103145873 B CN103145873 B CN 103145873B CN 201110401667 A CN201110401667 A CN 201110401667A CN 103145873 B CN103145873 B CN 103145873B
- Authority
- CN
- China
- Prior art keywords
- chitin
- pressure
- deacetylation
- solution
- value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种几丁质去乙酰化的方法,尤涉及一种以瞬间释压使几丁质去乙酰化的方法。The invention relates to a method for deacetylating chitin, in particular to a method for deacetylating chitin by instantaneous pressure release.
背景技术 Background technique
几丁质(chitin)及几丁聚醣(chitosan)是一种多功能、对环境友善、具有生物兼容性的现代材料,可应用的范围十分广泛,如农业、食品/营养、生物医药、材料科学、化妆品、废水处理、制纸、纺织等领域,故全世界无论是发达或发展中的国家均对此等物质积极进行研究。请参阅图1,其为几丁质的化学结构式示意图。几丁质是以N-乙酰葡萄胺糖为单体,且以β-1,4键结而成的高分子聚合物,存在于节肢动物的外骨骼、鱿鱼软骨及真菌的细胞壁中。虽然几丁质在自然界中含量丰富,且具有物理、化学性质稳定等优点,但其乙酰基易形成分子内/分子间氢键而形成紧密的结晶区域结构,使得几丁质在一般溶剂中的溶解度都很低,不利于产业利用。Chitin and chitosan are multifunctional, environmentally friendly, and biocompatible modern materials that can be used in a wide range of applications, such as agriculture, food/nutrition, biomedicine, materials Science, cosmetics, wastewater treatment, papermaking, textiles and other fields, so all countries in the world, whether developed or developing, are actively conducting research on these substances. Please refer to Figure 1, which is a schematic diagram of the chemical structural formula of chitin. Chitin is a high molecular polymer composed of N-acetylglucosamine sugar as a monomer and linked by β-1,4. It exists in the exoskeleton of arthropods, squid cartilage and the cell wall of fungi. Although chitin is abundant in nature and has the advantages of stable physical and chemical properties, its acetyl group is easy to form intramolecular/intermolecular hydrogen bonds to form a compact crystal domain structure, making chitin in general solvents The solubility is very low, which is not conducive to industrial utilization.
因此,如何有效打断几丁质上乙酰基和氮原子间的键结为产业上一个重要的课题。几丁质经去乙酰作用而制得的衍生物称为几丁聚醣,去乙酰化单体(葡萄胺糖)与非去乙酰化单体(N-乙酰葡萄胺糖)的比值越高,则该几丁聚醣分子越容易溶解于弱酸,而能显著提升其在产业上的应用性。Therefore, how to effectively break the bond between the acetyl group and the nitrogen atom on chitin is an important issue in the industry. The derivative of chitin obtained by deacetylation is called chitosan, and the higher the ratio of deacetylated monomer (glucosamine sugar) to non-deacetylated monomer (N-acetylglucosamine sugar), The easier the chitosan molecule is to dissolve in weak acid, the industrial applicability can be significantly improved.
目前几丁质去乙酰化的方法有微生物法、酵素法及热碱法等。微生物法和酵素法分别利用微生物和几丁质去乙酰酵素(Chitindeacetylase)对几丁质进行去乙酰化反应。这两种生物方法不会有几丁质分子链键结被打断之虞,也不会有严重的化学废液污染问题,但作用时间长,且产率及反应条件受限于微生物或酵素的耐受性,量产难度较高,因而甚少作为大量生产几丁聚醣的方法。Currently, chitin deacetylation methods include microbial method, enzyme method and hot alkali method. The microbial method and the enzyme method respectively use microorganisms and chitin deacetylase (Chitindeacetylase) to deacetylate chitin. These two biological methods will not have the risk of breaking the chitin molecular chain bonds, and will not have serious chemical waste pollution problems, but the action time is long, and the yield and reaction conditions are limited by microorganisms or enzymes Tolerance, mass production is difficult, so it is rarely used as a method for mass production of chitosan.
热碱法为目前制备几丁聚醣的主要商业方法,其是利用高温强碱对几丁质进行去乙酰化反应。其中,高浓度碱液(一般为30~60%NaOH)在溶剂中解离出大量带负电荷的氢氧根离子(OH-),该离子取代几丁质乙酰基上的氧原子而成为质子接收者,进而破坏几丁质分子内/分子间氢键及结晶区域结构,使乙酰基及胺基间的键结更容易与大量的氢氧根离子接触,而在高温下(一般为100~130℃)进行电子攻击及断裂的反应。The hot alkaline method is currently the main commercial method for preparing chitosan, which uses high temperature and strong alkali to deacetylate chitin. Among them, high-concentration lye (generally 30-60% NaOH) dissociates a large number of negatively charged hydroxide ions (OH - ) in the solvent, and the ions replace the oxygen atoms on the chitin acetyl group to become protons Receiver, and then destroy the intramolecular/intermolecular hydrogen bond and crystallization domain structure of chitin, making the bond between acetyl group and amine group more easily contact with a large number of hydroxide ions, and at high temperature (generally 100~ 130°C) for electron attack and fragmentation reactions.
此外,有文献指出适当的压力(约1~20PSIG)可促使更多的氢氧根离子及水分子进入几丁质结晶区域中,益于破坏氢键及促进乙酰胺基内的电子攻击反应,因而能进一步提升几丁质去乙酰化的程度。相较于微生物法及酵素法,热碱法虽然具有反应快速、反应变量少、去乙酰化程度高等优点,然而,此法会产生大量的废液,包括高浓度废碱液和水洗产物至中性的水洗废液,另外,热碱法除了使用大量氢氧化钠、纯水及处理废液造成的巨大成本外,还易于产生污染环境的不利后果。In addition, some literature pointed out that appropriate pressure (about 1-20PSIG) can promote more hydroxide ions and water molecules to enter the chitin crystal region, which is beneficial to destroy hydrogen bonds and promote electron attack reactions in acetamide groups. Therefore, the degree of chitin deacetylation can be further enhanced. Compared with the microbial method and the enzyme method, although the hot alkali method has the advantages of rapid reaction, less reaction variables, and a high degree of deacetylation, however, this method will produce a large amount of waste liquid, including high-concentration spent alkali liquid and water-washed products. In addition, in addition to the huge cost caused by the use of a large amount of sodium hydroxide, pure water and waste liquid treatment, the hot alkali method is also prone to adverse consequences of polluting the environment.
因此,有必要发展一种几丁质去乙酰化的新方法,具有反应快速、反应变量少,且不会产生大量废液而污染环境从而造成环保问题,并能兼顾操作简单、设备费低、降低成本的目的。Therefore, it is necessary to develop a new method for deacetylation of chitin, which has the advantages of rapid response, few reaction variables, and will not produce a large amount of waste liquid to pollute the environment and cause environmental protection problems, and can take into account simple operation, low equipment cost, The purpose of reducing costs.
发明内容 Contents of the invention
本发明要解决的技术问题在于,针对现有技术存在的上述不足,提供一种可以在中性环境下使几丁质快速去乙酰化的方法。The technical problem to be solved by the present invention is to provide a method for rapidly deacetylating chitin in a neutral environment, aiming at the above-mentioned deficiencies in the prior art.
本发明要解决的技术问题在于,针对现有技术存在的上述不足,提供一种兼具环保及成本低廉等优点的几丁质去乙酰化的方法。The technical problem to be solved by the present invention is to provide a chitin deacetylation method that has the advantages of environmental protection and low cost in view of the above-mentioned deficiencies in the prior art.
本发明要解决的技术问题在于,针对现有技术存在的上述不足,提供一种反应变量少且操作简单的几丁质去乙酰化的方法。The technical problem to be solved by the present invention is to provide a method for deacetylation of chitin with few reaction variables and simple operation in view of the above-mentioned deficiencies in the prior art.
本发明解决其技术问题所采用的技术方案是提供一种几丁质去乙酰化的方法,该方法至少包括下列步骤:The technical solution adopted by the present invention to solve the technical problems is to provide a method for chitin deacetylation, which at least includes the following steps:
(a)调整几丁质的水分至一预定含水量;(a) adjusting the moisture content of chitin to a predetermined moisture content;
(b)置入该几丁质至一密闭容器中;(b) putting the chitin into a closed container;
(c)加热该密闭容器至一预定温度,而使该密闭容器中的压力至一第一压力值;以及(c) heating the closed container to a predetermined temperature so that the pressure in the closed container reaches a first pressure value; and
(d)释放该密闭容器中的压力,而使该密闭容器中的压力降至一第二压力值;(d) releasing the pressure in the closed container so that the pressure in the closed container drops to a second pressure value;
其中,于该密闭容器中的压力自该第一压力值降至该第二压力值的过程中,将使该几丁质中的水分快速蒸发而打断该几丁质乙酰基和氮原子间的共价键。Wherein, when the pressure in the airtight container drops from the first pressure value to the second pressure value, the water in the chitin will evaporate rapidly to break the gap between the chitin acetyl group and the nitrogen atom. covalent bond.
较佳地,该步骤(a)至少包括下列步骤:Preferably, the step (a) includes at least the following steps:
(a1)浸泡几丁质于一溶液中;(a1) soaking chitin in a solution;
(a2)滤除该溶液,而保留该几丁质;以及(a2) filtering off the solution while retaining the chitin; and
(a3)调降该几丁质的水分至该预定含水量。(a3) reducing the moisture content of the chitin to the predetermined moisture content.
较佳地,该步骤(a3)中,是在50℃条件下烘干而调降该几丁质的水分至该预定含水量。Preferably, in the step (a3), the moisture of the chitin is lowered to the predetermined moisture content by drying at 50°C.
较佳地,该密闭容器为一压力容器,且该第一压力值大于表压1kg/cm2。Preferably, the airtight container is a pressure container, and the first pressure value is greater than the gauge pressure of 1 kg/cm 2 .
较佳地,该压力容器为膨发枪,且该第一压力值介于表压1~20kg/cm2。Preferably, the pressure vessel is an expansion gun, and the first pressure value is between 1-20 kg/cm 2 gauge pressure.
较佳地,该预定温度至少为100℃。Preferably, the predetermined temperature is at least 100°C.
较佳地,该几丁质的该预定含水量介于10~90%。Preferably, the predetermined water content of the chitin is between 10% and 90%.
较佳地,该步骤(a1)中,该溶液为水溶液。Preferably, in the step (a1), the solution is an aqueous solution.
较佳地,该水溶液的pH值至少为6。Preferably, the pH of the aqueous solution is at least 6.
较佳地,该水溶液的pH值介于6~8。Preferably, the pH value of the aqueous solution is between 6-8.
较佳地,该几丁质为α几丁质、β几丁质以及γ几丁质中的至少任一者。Preferably, the chitin is at least any one of α-chitin, β-chitin and γ-chitin.
本发明还提供一种几丁质去乙酰化的方法,该方法至少包括下列步骤:The present invention also provides a method for chitin deacetylation, which at least includes the following steps:
(a)置入几丁质至一密闭容器中;(a) put chitin into a closed container;
(b)调控该密闭容器中的压力至一第一压力值;以及(b) regulating the pressure in the closed container to a first pressure value; and
(c)释放该密闭容器中的压力,而使该密闭容器中的压力降至一第二压力值;(c) releasing the pressure in the closed container so that the pressure in the closed container drops to a second pressure value;
其中,于该密闭容器中的压力自该第一压力值降至该第二压力值的过程中,将使该几丁质中的水分快速蒸发而打断该几丁质乙酰基和氮原子间的共价键。Wherein, when the pressure in the airtight container drops from the first pressure value to the second pressure value, the water in the chitin will evaporate rapidly to break the gap between the chitin acetyl group and the nitrogen atom. covalent bond.
较佳地,该密闭容器为一压力容器,且该第一压力值大于表压1kg/cm2。Preferably, the airtight container is a pressure container, and the first pressure value is greater than the gauge pressure of 1 kg/cm 2 .
较佳地,该压力容器为膨发枪,且该第一压力值介于表压1~20kg/cm2。Preferably, the pressure vessel is an expansion gun, and the first pressure value is between 1-20 kg/cm 2 gauge pressure.
较佳地,于该步骤(b)中,是以加热至一预定温度的方式而调控该密闭容器的压力至该第一压力值。Preferably, in the step (b), the pressure of the airtight container is regulated to the first pressure value by heating to a predetermined temperature.
较佳地,该预定温度至少为100℃。Preferably, the predetermined temperature is at least 100°C.
较佳地,该步骤(a)之前更包括步骤:Preferably, the step (a) further includes steps before:
(a1)浸泡该几丁质于一溶液中。(a1) Soaking the chitin in a solution.
较佳地,该步骤(a1)与该步骤(a)之间,更包括步骤:Preferably, between the step (a1) and the step (a), further include steps:
(a2)滤除该溶液,而保留该几丁质。(a2) Filtering off the solution while retaining the chitin.
较佳地,该步骤(a2)与该步骤(a)之间,更包括步骤:Preferably, between the step (a2) and the step (a), further include steps:
(a3)调降该几丁质的水分至一预定含水量。(a3) reducing the moisture content of the chitin to a predetermined moisture content.
较佳地,于该步骤(a3)中,该几丁质的该预定含水量介于10~90%。Preferably, in the step (a3), the predetermined water content of the chitin is between 10% and 90%.
较佳地,于该步骤(a1)中,该溶液的pH值至少为6。Preferably, in the step (a1), the pH of the solution is at least 6.
较佳地,于该步骤(a1)中,该溶液的pH值介于6~8。Preferably, in the step (a1), the pH of the solution is between 6-8.
较佳地,该几丁质为α几丁质、β几丁质以及γ几丁质中的至少任一者。Preferably, the chitin is at least any one of α-chitin, β-chitin and γ-chitin.
本发明利用在高压下瞬间释压所产生的强大蒸气压,可达到去乙酰化的效果,且作用时不必使用大量的碱液,从而大量节省处理废碱液及水洗废液的成本,并避免废液对环境造成的污染,故本发明几丁质去乙酰化的方法具有可大量处理、反应快速、反应变量少、操作简单、成本低廉且可兼顾环保的优点。The present invention utilizes the strong vapor pressure generated by instantaneous pressure release under high pressure to achieve the effect of deacetylation, and does not need to use a large amount of lye during the action, thereby greatly saving the cost of treating spent lye and washing waste liquid, and avoiding Waste liquid pollutes the environment, so the chitin deacetylation method of the present invention has the advantages of large-scale treatment, rapid reaction, less reaction variables, simple operation, low cost and environmental protection.
附图说明 Description of drawings
图1是几丁质的化学结构式示意图。Figure 1 is a schematic diagram of the chemical structural formula of chitin.
图2是本发明几丁质去乙酰化的方法第一较佳实施例的方块流程示例图。Fig. 2 is an example diagram of the block flow of the first preferred embodiment of the chitin deacetylation method of the present invention.
图3是本发明几丁质去乙酰化的方法第二较佳实施例的方块流程示例图。Fig. 3 is an example diagram of the block flow of the second preferred embodiment of the chitin deacetylation method of the present invention.
图4是本发明第一较佳实施方法与第二较佳实施方法中所示的密闭容器的一具体实施概念示例图。Fig. 4 is a schematic illustration of a specific implementation concept of the airtight container shown in the first preferred implementation method and the second preferred implementation method of the present invention.
具体实施方式 detailed description
鉴于现有技术的缺陷,本发明提供一种几丁质去乙酰化的新方法,是利用高压急速恢复至常压时,几丁质微粒结构内的水分全部在一瞬间蒸发,造成微粒结构内产生强大的蒸气压而向四面八方快速膨胀,在这个过程中,微粒结构内较弱的键结(例如氢键、乙酰基和氮原子间的共价键)会被打断,蒸气压则藉由这些断裂的孔隙宣泄。In view of the defects of the prior art, the present invention provides a new method for deacetylation of chitin, which uses high pressure to quickly return to normal pressure, and all the water in the chitin particle structure evaporates in an instant, resulting in Generates a strong vapor pressure and expands rapidly in all directions. During this process, the weaker bonds in the particle structure (such as hydrogen bonds, covalent bonds between acetyl groups and nitrogen atoms) will be broken, and the vapor pressure will be increased by These fractured pores vent.
申言之,在实验中可观察到经高压急速恢复至常压的几丁质,其去乙酰化程度显著高于未经急速释压的几丁质(p<0.05)。以电子显微镜观察后发现,在高压急速恢复至常压后,几丁质发生颗粒变小的情形,且每个小颗粒上都呈现多孔隙的现象,证明在释压的瞬间确实发生急剧的膨胀现象,使得维系微粒结构的作用力被破坏,造成微粒结构被胀破成许多更小的颗粒并密布无数小孔隙的结果。In other words, it can be observed in the experiment that the degree of deacetylation of chitin that has been rapidly restored to normal pressure after high pressure is significantly higher than that of chitin that has not been rapidly released (p<0.05). Observation with an electron microscope revealed that after the high pressure was rapidly returned to normal pressure, the chitin particles became smaller, and each small particle showed a phenomenon of porosity, which proved that the rapid expansion did occur at the moment of pressure release. Phenomenon, the force that maintains the particle structure is destroyed, causing the particle structure to be broken into many smaller particles and densely covered with countless small pores.
请参阅图2,其为本发明一种几丁质去乙酰化的方法于第一较佳实施例中的方块流程图。本发明一种几丁质去乙酰化的较佳实施方法至少包括:Please refer to FIG. 2 , which is a block flow diagram of a chitin deacetylation method in a first preferred embodiment of the present invention. A preferred implementation method of chitin deacetylation of the present invention at least includes:
步骤S1:调整几丁质的水分至预定含水量;Step S1: adjusting the water content of chitin to a predetermined water content;
步骤S2:置入几丁质至密闭容器1中;Step S2: put chitin into the airtight container 1;
步骤S3:加热至预定温度,使密闭容器1中的压力至第一压力值;以及Step S3: heating to a predetermined temperature, so that the pressure in the airtight container 1 reaches the first pressure value; and
步骤S4:释放密闭容器1中的压力,使密闭容器1中的压力降至第二压力值而打断几丁质的乙酰基和氮原子间的共价键A。Step S4: releasing the pressure in the airtight container 1, reducing the pressure in the airtight container 1 to a second pressure value to break the covalent bond A between the acetyl group and the nitrogen atom of chitin.
其中,步骤S1至少包括:Wherein, step S1 includes at least:
步骤a1:浸泡几丁质于溶液中;Step a1: soaking chitin in the solution;
步骤a2:滤除溶液,而保留几丁质;以及Step a2: filtering off the solution while retaining chitin; and
步骤a3:调降几丁质的水分至预定含水量。Step a3: reducing the water content of chitin to a predetermined water content.
于本较佳实施例中,步骤S1用以调节几丁质微粒结构内的含水量。其中,步骤a1将几丁质浸泡于溶液中,会使得几丁质微粒结构内部充满溶液而膨润胀大,该溶液可以是纯水、中性水溶液、微酸性水溶液、碱性水溶液,或其它液态的溶液;但不以此为限。In this preferred embodiment, step S1 is used to adjust the water content in the chitin particle structure. Wherein, in step a1, soaking chitin in the solution will cause the inside of the chitin particle structure to be filled with solution and swell and expand. The solution can be pure water, neutral aqueous solution, slightly acidic aqueous solution, alkaline aqueous solution, or other Liquid solutions; but not limited to.
步骤a2藉由网筛或其它方法滤除多余的溶液,而保留几丁质,以便进一步调整几丁质微粒结构内外的水分含量。步骤a3可藉由50℃烘箱或其它温度、方式调降几丁质的水分至预定含水量,且该预定含水量以10~90%为佳。In step a2, the excess solution is filtered out by mesh sieve or other methods, and the chitin is retained, so as to further adjust the water content inside and outside the chitin particle structure. In step a3, the water content of chitin can be reduced to a predetermined water content by means of an oven at 50°C or other temperature methods, and the predetermined water content is preferably 10-90%.
需特别说明的是,步骤S1在后续去乙酰化效果上扮演重要角色,无论是膨润的程度或几丁质微粒结构内外水分的含量都会影响微粒结构的体积、释压后蒸气的多寡、蒸气压的大小及是否造成几丁质发生褐化烧焦的现象,因此,需确实评估步骤S1中各个子步骤的作用条件,以期达到最佳的去乙酰化效果。It should be noted that step S1 plays an important role in the subsequent deacetylation effect. Whether it is the degree of swelling or the water content inside and outside the chitin particle structure, it will affect the volume of the particle structure, the amount of steam after pressure release, and the amount of steam. Therefore, it is necessary to evaluate the action conditions of each sub-step in step S1 in order to achieve the best deacetylation effect.
再则,步骤S2将几丁质置入密闭容器1中,以进行后续升压的步骤。该密闭容器1可以为膨发枪(请先行配合参阅图4所示),抑或其它具有瞬间释压安全防护的压力容器,但不以此为限。Furthermore, step S2 puts chitin into the airtight container 1 for the subsequent step of boosting the pressure. The airtight container 1 can be an expansion gun (please refer to FIG. 4 for cooperation first), or other pressure vessels with instantaneous pressure release safety protection, but it is not limited thereto.
且,步骤S3将密闭容器1加热至预定温度,使密闭容器1中的压力达到第一压力值。其中,该预定温度需大于或等于溶液在大气压(表压为0kg/cm2)下的沸点,以藉由溶液蒸发时产生的蒸气使密闭容器1中的压力达到第一压力值。例如,溶液为纯水时,该预定温度需大于或等于100℃。此外,第一压力值应大于大气压力,其压力越大则去乙酰化的效果越好,但过大也可能会造成几丁质分子链断裂的降解反应发生。Moreover, step S3 heats the airtight container 1 to a predetermined temperature, so that the pressure in the airtight container 1 reaches a first pressure value. Wherein, the predetermined temperature needs to be greater than or equal to the boiling point of the solution at atmospheric pressure (gauge pressure is 0 kg/cm 2 ), so that the pressure in the airtight container 1 reaches the first pressure value by the vapor generated when the solution evaporates. For example, when the solution is pure water, the predetermined temperature must be greater than or equal to 100°C. In addition, the first pressure value should be greater than atmospheric pressure, the greater the pressure, the better the effect of deacetylation, but too high may cause the degradation reaction of chitin molecular chain breakage.
又,步骤S4瞬间释放密闭容器1中的压力,使密闭容器1中的压力降至第二压力值而打断几丁质的乙酰基和氮原子间的共价键A。其中该第二压力值可以为大气压力或其它小于第一压力值的压力。在安全性及设备许可的情况之下,第二压力值甚至可以小于大气压力(例如,将密闭容器置于一负压或接近真空的环境下,使密闭容器释压后达到一小于大气压力的第二压力值)。Also, step S4 releases the pressure in the airtight container 1 instantaneously, reducing the pressure in the airtight container 1 to a second pressure value to break the covalent bond A between the acetyl group of chitin and the nitrogen atom. Wherein the second pressure value may be atmospheric pressure or other pressures lower than the first pressure value. Under the condition of safety and equipment permission, the second pressure value can even be less than atmospheric pressure (for example, the airtight container is placed in a negative pressure or under the environment of near vacuum, and after the airtight container is depressurized, it reaches a pressure lower than the atmospheric pressure. second pressure value).
本发明更提供一第二较佳实施例。请参阅图3,其为本发明一种几丁质去乙酰化的方法于第二较佳实施例中的方块流程图。本发明一种几丁质去乙酰化的另一较佳实施方法至少包括:The present invention further provides a second preferred embodiment. Please refer to FIG. 3 , which is a block flow diagram of a chitin deacetylation method in a second preferred embodiment of the present invention. Another preferred implementation method of chitin deacetylation of the present invention at least includes:
步骤S11:置入几丁质至密闭容器111中;Step S11: putting chitin into the airtight container 111;
步骤S12:调控密闭容器111中的压力至第一压力值;Step S12: regulating the pressure in the airtight container 111 to a first pressure value;
步骤S13:释放密闭容器111中的压力,使密闭容器111中的压力降至第二压力值而打断几丁质的乙酰基和氮原子间的共价键A’。Step S13: releasing the pressure in the airtight container 111, reducing the pressure in the airtight container 111 to a second pressure value to break the covalent bond A' between the acetyl group of chitin and the nitrogen atom.
第二较佳实施例与第一较佳实施例中各步骤的方法、条件及顺序都一致,唯一差别只在于第一较佳实施例包括一调整几丁质的水分至预定含水量的步骤S1,且步骤S3以加热的方式使密闭容器1升压;当然,任何本领域普通技术人员可为任意的均等变化,并不以上述的较佳实施步骤的内容为限。The method, condition and sequence of each step in the second preferred embodiment are the same as those in the first preferred embodiment, the only difference is that the first preferred embodiment includes a step S1 of adjusting the moisture content of chitin to a predetermined moisture content , and step S3 increases the pressure of the airtight container 1 by means of heating; of course, any person skilled in the art can make any equal changes, and is not limited to the content of the above-mentioned preferred implementation steps.
至于第二较佳实施例,则并未包括调整几丁质的水分的步骤,仅利用几丁质原料中含有的水分即为已足,且步骤S12不限于以加热方式升压,亦可以为其它的升压方式,例如压缩密闭容器111的体积等。As for the second preferred embodiment, it does not include the step of adjusting the water content of chitin, and it is sufficient to only use the water contained in the chitin raw material, and step S12 is not limited to increasing the pressure by heating, and can also be Other boosting methods include compressing the volume of the airtight container 111 and the like.
请参见下列表一,其为α-几丁质经爆炸性膨发后去乙酰程度的变化。表一由上至下分别呈现α-几丁质经六组不同条件处理后,其去乙酰程度的结果。在第一组实验中,α-几丁质未经任何调整水分、升压、pH值或瞬间释压的处理,结果显示其去乙酰程度为25.2±1.9%。在第二组实验中,先将α-几丁质浸泡于pH值为6.5的纯水中1小时,再滤除多余的水分而保留α-几丁质,此时α-几丁质水分含量为60%。将α-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压6kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为25.3±0.8%,与第一组的结果相比无显著差异。在第三组实验中,先将α-几丁质浸泡于pH值为6.5的纯水中1小时,再滤除多余的水分而保留α-几丁质,此时α-几丁质水分含量为60%。将α-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压9kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为27.3±2.5%,与第一组的结果相比无显著差异。Please refer to Table 1 below, which shows the changes in the degree of deacetylation of α-chitin after explosive expansion. Table 1 presents the results of the deacetylation degree of α-chitin treated with six groups of different conditions from top to bottom. In the first set of experiments, α-chitin was not treated with any adjustment of moisture, pressure increase, pH value or instantaneous pressure release, and the results showed that its degree of deacetylation was 25.2±1.9%. In the second set of experiments, α-chitin was first soaked in pure water with a pH value of 6.5 for 1 hour, and then the excess water was filtered off to retain α-chitin. At this time, the water content of α-chitin 60%. Put α-chitin into the expansion gun, and heat to make the pressure in the expansion gun reach the gauge pressure of 6kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The result shows that the degree of deacetylation is 25.3±0.8%, which has no significant difference compared with the result of the first group. In the third group of experiments, α-chitin was first soaked in pure water with a pH value of 6.5 for 1 hour, and then the excess water was filtered to retain α-chitin. At this time, the water content of α-chitin 60%. Put α-chitin into the expansion gun, and heat to make the pressure in the expansion gun reach the gauge pressure of 9kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The results showed that the degree of deacetylation was 27.3±2.5%, which was not significantly different from the results of the first group.
在第四组实验中,先将α-几丁质浸泡于pH值为6.5的纯水中1小时,再滤除多余的水分而保留α-几丁质,此时α-几丁质水分含量为60%。将α-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压12kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为38.8±1.5%,与第一组的结果相比有显著差异(p<0.05)。在第五组实验中,依序将α-几丁质浸泡于pH值为6.5的纯水中1小时,滤除多余的水分而保留α-几丁质,并以50℃烘箱干燥3小时,此时α-几丁质水分含量为47%。将α-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压9kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为30.2±3.4%,与第一组的结果相比有显著差异(p<0.05)。在第六组实验中,先将α-几丁质浸泡于pH值为9.0的氢氧化钠水溶液中1小时,再滤除多余的水分而保留α-几丁质,此时α-几丁质水分含量为60%。将α-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压9kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为31.2±1.6%,与第一组的结果相比有显著差异(p<0.05)。In the fourth set of experiments, α-chitin was first soaked in pure water with a pH value of 6.5 for 1 hour, and then the excess water was filtered off to retain α-chitin. At this time, the water content of α-chitin 60%. Put α-chitin into the expansion gun, and heat to make the pressure in the expansion gun reach the gauge pressure of 12kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The result shows that the degree of deacetylation is 38.8±1.5%, which is significantly different from the result of the first group (p<0.05). In the fifth set of experiments, α-chitin was sequentially soaked in pure water with a pH value of 6.5 for 1 hour, excess water was filtered off to retain α-chitin, and oven-dried at 50°C for 3 hours, At this time, the moisture content of α-chitin was 47%. Put α-chitin into the expansion gun, and heat to make the pressure in the expansion gun reach the gauge pressure of 9kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The result shows that the degree of deacetylation is 30.2±3.4%, which is significantly different from the result of the first group (p<0.05). In the sixth group of experiments, α-chitin was first soaked in sodium hydroxide aqueous solution with a pH value of 9.0 for 1 hour, and then the excess water was filtered off to retain α-chitin. At this time, α-chitin The moisture content is 60%. Put α-chitin into the expansion gun, and heat to make the pressure in the expansion gun reach the gauge pressure of 9kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The result shows that the degree of deacetylation is 31.2±1.6%, which is significantly different from the result of the first group (p<0.05).
由表一第一组至第四组的结果得知,以爆炸性膨发去除α-几丁质乙酰基的方法中,α-几丁质去乙酰化的程度与膨发枪释压前的压力强度程正相关,即释压前压力强度越强则α-几丁质去乙酰化程度越高,且释压前表压为12kg/cm2以上的效果较显著。由表一第三组及第五组的结果得知,以爆炸性膨发去除α-几丁质乙酰基的方法中,α-几丁质去乙酰化的程度与α-几丁质微粒结构中的含水量有关。由表一第三组及第六组的结果得知,以爆炸性膨发去除α-几丁质乙酰基的方法中,α-几丁质去乙酰化的程度与α-几丁质微粒结构中的水分pH值有关,在偏碱性的条件下其去乙酰化的程度较高。综合以上结果可知,以爆炸性膨发去除α-几丁质乙酰基的方法中,α-几丁质去乙酰化的程度与释压前的压力、α-几丁质的含水量、α-几丁质内水分的pH值有关。经爆炸性膨发后,其去乙酰化程度由25.2±1.9%增加至25.3±0.8%~38.8±1.5%,去乙酰程度最多约可增加13%。From the results of the first group to the fourth group in Table 1, it is known that in the method of removing α-chitin acetyl group by explosive expansion, the degree of deacetylation of α-chitin is related to the pressure before the expansion gun is released. The intensity range is positively correlated, that is, the stronger the pressure intensity before pressure release, the higher the deacetylation degree of α-chitin, and the effect is more significant when the gauge pressure before pressure release is above 12kg/cm 2 . From the results of the third group and the fifth group in Table 1, in the method of removing the acetyl group of α-chitin by explosive expansion, the degree of deacetylation of α-chitin is related to the particle structure of α-chitin. related to the moisture content. From the results of the third group and the sixth group in Table 1, in the method of removing the acetyl group of α-chitin by explosive expansion, the degree of deacetylation of α-chitin is related to the particle structure of α-chitin. It is related to the pH value of the water, and the degree of deacetylation is higher under alkaline conditions. Based on the above results, it can be seen that in the method of removing α-chitin acetyl groups by explosive expansion, the degree of deacetylation of α-chitin is related to the pressure before pressure release, the water content of α-chitin, and the It is related to the pH value of the water in the butyl. After explosive expansion, the degree of deacetylation increased from 25.2±1.9% to 25.3±0.8%-38.8±1.5%, and the degree of deacetylation could increase by about 13%.
表一、α-几丁质经爆炸性膨发后去乙酰程度的变化。Table 1. Changes in deacetylation degree of α-chitin after explosive expansion.
*未经处理的几丁质 * unprocessed chitin
以上数据为5次实验的结果,以平均值±标准差表示。a-c不同字母代表两组数据之间具有显著差异(p<0.05);若有相同字母则代表两组数据之间不具有显著差异。The above data are the results of 5 experiments, expressed as mean ± standard deviation. Different letters in a-c represent significant differences between the two groups of data (p<0.05); same letters represent no significant differences between the two groups of data.
请再参见下列表二,其为β-几丁质经爆炸性膨发后去乙酰程度的变化。表二由上至下分别呈现β-几丁质经七组不同条件处理后,其去乙酰程度的结果。在第一组实验中,β-几丁质未经任何调整水分、升压、pH值或瞬间释压的处理,结果显示其去乙酰程度为32.2±1.4%。在第二组实验中,依序将β-几丁质浸泡于pH值为6.5的纯水中1小时,滤除多余的水分而保留β-几丁质,再以50℃烘箱干燥12小时,此时β-几丁质水分含量为30%。将β-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压10kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为33.3±1.1%,与第一组的结果相比无显著差异。在第三组实验中,依序将β-几丁质浸泡于pH值为6.5的纯水中1小时,滤除多余的水分而保留β-几丁质,再以50℃烘箱干燥6小时,此时β-几丁质水分含量为60%。将β-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压10kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为33.8±2.5%,与第一组的结果相比无显著差异。在第四组实验中,先将β-几丁质浸泡于pH值为6.5的纯水中1小时,再滤除多余的水分而保留β-几丁质,此时β-几丁质水分含量为80%。将β-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压10kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为35.2±1.6%,与第一组的结果相比无显著差异。Please refer to Table 2 below again, which is the change in deacetylation degree of β-chitin after explosive expansion. Table 2 presents the results of the degree of deacetylation of β-chitin from top to bottom after being treated with seven groups of different conditions. In the first set of experiments, β-chitin was not treated with any adjustment of moisture, pressure increase, pH value or instantaneous pressure release, and the results showed that its degree of deacetylation was 32.2±1.4%. In the second set of experiments, β-chitin was sequentially soaked in pure water with a pH value of 6.5 for 1 hour, excess water was filtered off to retain β-chitin, and then oven-dried at 50°C for 12 hours. At this time, the moisture content of β-chitin was 30%. Put β-chitin into the expansion gun and heat to make the pressure in the expansion gun reach the gauge pressure of 10kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The results showed that the degree of deacetylation was 33.3±1.1%, which was not significantly different from the results of the first group. In the third set of experiments, β-chitin was sequentially soaked in pure water with a pH value of 6.5 for 1 hour, excess water was filtered off to retain β-chitin, and then oven-dried at 50°C for 6 hours. At this time, the moisture content of β-chitin was 60%. Put β-chitin into the expansion gun and heat to make the pressure in the expansion gun reach the gauge pressure of 10kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The results showed that the degree of deacetylation was 33.8±2.5%, which was not significantly different from the results of the first group. In the fourth set of experiments, β-chitin was first soaked in pure water with a pH value of 6.5 for 1 hour, and then the excess water was filtered to retain β-chitin. At this time, the moisture content of β-chitin 80%. Put β-chitin into the expansion gun and heat to make the pressure in the expansion gun reach the gauge pressure of 10kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The result shows that the degree of deacetylation is 35.2±1.6%, which is not significantly different from the result of the first group.
在第五组实验中,将β-几丁质浸泡于pH值为6.5的纯水中1小时,滤除多余的水分而保留β-几丁质,此时β-几丁质水分含量为80%。将β-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压15kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为37.6±2.2%,与第一组的结果相比有显著差异(p<0.05)。在第六组实验中,先将β-几丁质浸泡于pH值为6.5的纯水中1小时,再滤除多余的水分而保留β-几丁质,此时β-几丁质水分含量为80%。将β-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压20kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为41.4±3.1%,与第一组的结果相比有显著差异(p<0.05)。在第七组实验中,先将β-几丁质浸泡于pH值为9.0的氢氧化钠水溶液中1小时,再滤除多余的水分而保留β-几丁质,此时β-几丁质水分含量为80%。将β-几丁质置入膨发枪中,加热使膨发枪内的压力达到表压10kg/cm2。瞬间打开膨发枪槽盖,达到突然释压的效果,结果显示其去乙酰程度为35.5±0.3%,与第一组的结果相比无显著差异。In the fifth set of experiments, β-chitin was soaked in pure water with a pH value of 6.5 for 1 hour, and the excess water was filtered to retain β-chitin. At this time, the moisture content of β-chitin was 80 %. Put β-chitin into the expansion gun and heat to make the pressure in the expansion gun reach the gauge pressure of 15kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The result shows that the degree of deacetylation is 37.6±2.2%, which is significantly different from the result of the first group (p<0.05). In the sixth group of experiments, β-chitin was first soaked in pure water with a pH value of 6.5 for 1 hour, and then the excess water was filtered to retain β-chitin. At this time, the moisture content of β-chitin 80%. Put β-chitin into the expansion gun and heat to make the pressure in the expansion gun reach the gauge pressure of 20kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The results showed that the degree of deacetylation was 41.4±3.1%, which was significantly different from the results of the first group (p<0.05). In the seventh group of experiments, β-chitin was first soaked in sodium hydroxide aqueous solution with a pH value of 9.0 for 1 hour, and then the excess water was filtered to retain β-chitin. At this time, β-chitin The moisture content is 80%. Put β-chitin into the expansion gun and heat to make the pressure in the expansion gun reach the gauge pressure of 10kg/cm 2 . Instantly open the tank cover of the expansion gun to achieve the effect of sudden pressure release. The results showed that the degree of deacetylation was 35.5±0.3%, which was not significantly different from the results of the first group.
由表二第一组、第四组至第六组的结果得知,以爆炸性膨发去除β-几丁质乙酰基的方法中,β-几丁质去乙酰化的程度与膨发枪释压前的压力强度程正相关,即释压前压力强度越强则β-几丁质去乙酰化程度越高,且释压前表压为15kg/cm2以上有显著效果。由表二第一组至第四组的结果得知,以爆炸性膨发去除β-几丁质乙酰基的方法中,β-几丁质去乙酰化的程度可能与β-几丁质微粒结构中的含水量有关。由表二第一组、第四组及第七组的结果得知,以爆炸性膨发去除β-几丁质乙酰基的方法中,β-几丁质去乙酰化的程度可能与β-几丁质含水量的pH值有关。综合以上结果可知,以爆炸性膨发去除β-几丁质乙酰基的方法中,β-几丁质去乙酰化的程度与释压前的压力有关,并可能与几丁质含水量及几丁质微粒结构中的水分pH值有关。经爆炸性膨发后,其去乙酰化程度由32.2±1.4%增加至33.3±1.1%~41.4±3.1%,去乙酰程度最多约可增加9%。From the results of the first group, the fourth group to the sixth group in Table 2, in the method of removing β-chitin acetyl group by explosive swelling, the degree of deacetylation of β-chitin is related to the swelling gun release method. The pressure intensity before pressure is positively correlated, that is, the stronger the pressure intensity before pressure release, the higher the deacetylation degree of β-chitin, and the gauge pressure before pressure release is above 15kg/cm 2 has a significant effect. From the results of the first group to the fourth group in Table 2, in the method of removing β-chitin acetyl group by explosive expansion, the degree of deacetylation of β-chitin may be related to the particle structure of β-chitin related to the moisture content. According to the results of the first group, the fourth group and the seventh group in Table 2, in the method of removing β-chitin acetyl group by explosive swelling, the degree of deacetylation of β-chitin may be the same as that of β-chitin The pH value of the water content of butin is related. Based on the above results, it can be seen that in the method of removing β-chitin acetyl groups by explosive expansion, the degree of deacetylation of β-chitin is related to the pressure before pressure release, and may be related to the water content of chitin and the chitin concentration. It is related to the pH value of the water in the particle structure. After explosive expansion, the degree of deacetylation increased from 32.2±1.4% to 33.3±1.1%-41.4±3.1%, and the degree of deacetylation increased by about 9%.
表二、β-几丁质经爆炸性膨发后去乙酰程度的变化。Table 2. Changes in deacetylation degree of β-chitin after explosive expansion.
*未经处理的几丁质 * unprocessed chitin
以上数据为5次实验的结果,以平均值±标准差表示。a-c不同字母代表两组数据之间具有显著差异(p<0.05);若有相同字母则代表两组数据之间不具有显著差异。The above data are the results of 5 experiments, expressed as mean ± standard deviation. Different letters in a-c represent significant differences between the two groups of data (p<0.05); same letters represent no significant differences between the two groups of data.
根据上述可知,本发明利用在高压下瞬间释压所产生的强大蒸气压,确实可达到去乙酰化的结果,且作用时不必使用大量的碱液,大量节省处理废碱液及水洗废液的成本,并避免废液对环境造成的污染,故本方法为一种可大量处理、反应快速、反应变量少、操作简单、成本低廉且可兼顾环保的几丁质去乙酰化新方法。According to the above, it can be known that the present invention utilizes the strong vapor pressure produced by the instantaneous pressure release under high pressure to achieve the result of deacetylation, and it is not necessary to use a large amount of lye during the action, which saves a lot of time spent on processing spent lye and washing waste. Therefore, this method is a new chitin deacetylation method that can be processed in large quantities, reacts quickly, has less reaction variables, is simple to operate, low in cost, and can take into account environmental protection.
至于,应用于前述第一较佳实施方法与第二较佳实施方法中所示的密闭容器1与密闭容器111,举例而言,其较佳具体实施结构可为图4所示的膨发枪10,且其至少包括:控制器11,压力传感器12,旋转槽13,加热器14及槽盖15等组件。其中,在以膨发枪10对几丁质进行爆炸性膨发的各种较佳实施例中,先将几丁质置入膨发枪10的旋转槽13中,闭锁旋转槽13,并使加热器14于加热至所设定的第一压力值(可由压力传感器12得知)后,瞬间打开槽盖15,以达到突然释压而使几丁质去乙酰化的目的。当然,图4所示的膨发枪仅为前述密闭容器的一较佳实施例,并不以此为限。As for the airtight container 1 and the airtight container 111 shown in the aforementioned first preferred implementation method and second preferred implementation method, for example, its preferred specific implementation structure can be the expansion gun shown in Figure 4 10, and it at least includes: a controller 11, a pressure sensor 12, a rotating tank 13, a heater 14 and a tank cover 15 and other components. Among them, in various preferred embodiments in which chitin is explosively expanded with the expanding gun 10, the chitin is first placed in the rotating groove 13 of the expanding gun 10, the rotating groove 13 is locked, and the heating After the device 14 is heated to the set first pressure value (which can be known by the pressure sensor 12), the tank cover 15 is opened instantly to achieve the purpose of deacetylating chitin by sudden pressure release. Of course, the expansion gun shown in FIG. 4 is only a preferred embodiment of the aforementioned airtight container, and is not limited thereto.
以上所述仅为本发明的较佳实施例及实验数据,并非用以限定本发明的权利要求范围,因此凡其它未脱离本发明所揭示的精神下所完成的等效改变或修饰,均应包含于本发明的范围内。The above descriptions are only preferred embodiments and experimental data of the present invention, and are not intended to limit the scope of the claims of the present invention. Therefore, all other equivalent changes or modifications that do not depart from the spirit disclosed in the present invention should be included within the scope of the present invention.
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110401667.9A CN103145873B (en) | 2011-12-06 | 2011-12-06 | Chitin deacetylation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110401667.9A CN103145873B (en) | 2011-12-06 | 2011-12-06 | Chitin deacetylation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103145873A CN103145873A (en) | 2013-06-12 |
CN103145873B true CN103145873B (en) | 2015-12-09 |
Family
ID=48544228
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201110401667.9A Expired - Fee Related CN103145873B (en) | 2011-12-06 | 2011-12-06 | Chitin deacetylation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103145873B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI740312B (en) * | 2019-12-18 | 2021-09-21 | 國立臺灣海洋大學 | Chitin aqueous solution and its obtaining method |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1179781A (en) * | 1995-03-25 | 1998-04-22 | 佛恩-帕沃林·罗迪阿公司 | Process for activating polysaccharides, polysaccharides produced by this process, and use thereof |
CN101775079A (en) * | 2009-12-07 | 2010-07-14 | 汪昔奇 | Method for pre-treating chitin raw material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0651724B2 (en) * | 1985-05-09 | 1994-07-06 | ライオン株式会社 | Process for producing activated chitin and chitosan |
-
2011
- 2011-12-06 CN CN201110401667.9A patent/CN103145873B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1179781A (en) * | 1995-03-25 | 1998-04-22 | 佛恩-帕沃林·罗迪阿公司 | Process for activating polysaccharides, polysaccharides produced by this process, and use thereof |
CN101775079A (en) * | 2009-12-07 | 2010-07-14 | 汪昔奇 | Method for pre-treating chitin raw material |
Also Published As
Publication number | Publication date |
---|---|
CN103145873A (en) | 2013-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | Dyes adsorption using a synthetic carboxymethyl cellulose-acrylic acid adsorbent | |
Singh et al. | Microwave induced KOH activation of guava peel carbon as an adsorbent for congo red dye removal from aqueous phase | |
CN101775079A (en) | Method for pre-treating chitin raw material | |
CN102180988B (en) | Method for preparing k-carrageenan with high gel strength from eucheuma | |
Xu et al. | Adsorption of Cu (ii) ions in aqueous solution by aminated lignin from enzymatic hydrolysis residues | |
CN102926251B (en) | Method for extracting cellulose from straw by adopting ionic liquid | |
Feng et al. | Synthesis and characterization of porous hydrogel based on lignin and polyacrylamide | |
CN104403018A (en) | Algal polysaccharide extraction method | |
CN103992488A (en) | CO2 Supercritical Fluid Carries Ionic Liquid to Improve Cellulose Solubility | |
CN102407097A (en) | Preparation method of hemicellulose-based heavy metal ion adsorbent | |
CN103145873B (en) | Chitin deacetylation method | |
CN106084259A (en) | A kind of preparation method of cellulose aquagel | |
CN111672482A (en) | A kind of preparation method of carboxymethyl hemicellulose/chitosan cross-linked spherical hydrogel | |
CN104327287A (en) | Preparation method of chitosan beads | |
CN101733002B (en) | PH-sensitive type cation regenerated cellulose composite film as well as preparation method and application thereof | |
TWI443110B (en) | Method of chitin deacetylation | |
TWI567089B (en) | Method of pretreating crab or shrip shells and method of preparing α-chitin | |
Xu et al. | Preparation and optimization of porous regenerated cellulose microspheres from cellulose tetraethyl-ammonium/urea solution for adsorption of cationic methylene blue dy | |
CN103233381A (en) | High efficiency composite precipitating agent and method for extracting cellulose | |
CN104418322B (en) | Utilize ionic liquid trapping carbon dioxide and the method extracting chitosan | |
CN102108101B (en) | Preparation method for natural polymer flocculant used for oil liquid purification | |
CN105725030A (en) | Method for effectively improving production performance in dehydrating and drying residual fruit processing solid matter | |
CN112480290A (en) | Preparation method of squid cartilage beta-chitosan | |
CN105601817A (en) | Green and environment-friendly method for preparing alkaline water-soluble chitosan derivative | |
CN103566909A (en) | Preparation method and application of citric acid cotton stalk skins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151209 Termination date: 20211206 |