WO2022143214A1 - 一种制备改性纤维素的方法及装置 - Google Patents

一种制备改性纤维素的方法及装置 Download PDF

Info

Publication number
WO2022143214A1
WO2022143214A1 PCT/CN2021/139048 CN2021139048W WO2022143214A1 WO 2022143214 A1 WO2022143214 A1 WO 2022143214A1 CN 2021139048 W CN2021139048 W CN 2021139048W WO 2022143214 A1 WO2022143214 A1 WO 2022143214A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
liquid
reaction kettle
circulation system
modified cellulose
Prior art date
Application number
PCT/CN2021/139048
Other languages
English (en)
French (fr)
Inventor
滕鲲
李长胤
刘涛
张燕
李同河
李茂丰
赵明
Original Assignee
山东一滕新材料股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 山东一滕新材料股份有限公司 filed Critical 山东一滕新材料股份有限公司
Publication of WO2022143214A1 publication Critical patent/WO2022143214A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/08—Alkali cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/08—Alkali cellulose
    • C08B1/10—Apparatus for the preparation of alkali cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B17/00—Apparatus for esterification or etherification of cellulose
    • C08B17/06—Apparatus for esterification or etherification of cellulose for making cellulose ethers

Definitions

  • the present application relates to a method and device for preparing modified cellulose.
  • HPMC Hydroxypropyl methyl cellulose
  • HEMC hydroxyethyl methyl cellulose
  • Cellulose ether reactors are divided into horizontal reactors or vertical reactors, which can be used alone as a reaction device, or with a cooler as a reaction device.
  • reaction kettle used alone is suitable for the slurry process, the etherifying agent is dissolved in an inert organic solvent, and the reaction pressure is generally low, below 0.6MPa.
  • this kind of process reaction kettle has small feeding amount, long reaction time and low production efficiency; the inert organic solvent needs to be recycled and reused, resulting in large pollution and high cost.
  • the reactor used with the cooler is suitable for the gas-solid process. There is no inert organic solvent in the reactor, and a large amount of etherifying agent and low-boiling by-products repeat the gasification-condensation process in the reactor and the cooler, and the reaction pressure is generally high. , up to 2.2-2.35MPa, which has higher requirements on the pressure resistance and sealing performance of the reaction equipment.
  • the embodiments of the present application provide a method for preparing modified cellulose, including the process of subjecting cellulose to an alkalization reaction and an etherification reaction to obtain modified cellulose, and placing the alkalized cellulose in a circulation In the flowing reaction solution, the reaction solution leaves the alkalized cellulose in a gaseous state, and then returns to the alkalized cellulose in a liquid state; the reaction solution is methyl chloride, alkylene oxide and dimethyl ether.
  • the reaction conditions of the etherification reaction are a gauge pressure of 0.2-1.0 MPa, a reaction time of 1.5-6 h, and a reaction temperature of 50-90°C.
  • the reaction condition of the etherification reaction is a gauge pressure of 0.4-0.6 MPa.
  • the parts by mass of each substance in the reaction solution are: alkylene oxide: 13-65 parts; methyl chloride: 80-140 parts; dimethyl ether: 60-80 parts.
  • the alkylene oxide is ethylene oxide and/or propylene oxide.
  • the concentration of liquid caustic soda is 40-60 wt %, and the mass ratio of cellulose to liquid caustic is 1:0.7-1.7.
  • the present application also discloses a device for preparing modified cellulose, comprising a reaction kettle, wherein the reaction kettle is provided with a solid-liquid space for reaction, and a solid-liquid space for accommodating the liquid from the solid-liquid space.
  • the gas-phase space of the overflowing gas is provided with an external circulation system outside the reaction kettle.
  • This application is used to prepare hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose and other substances from cellulose.
  • the liquid in the solid-liquid space is heated and vaporized, and first enters the gas-phase space.
  • the external circulation system includes a cooling module for cooling the gas overflowing from the gas phase space, and a liquid transporter that obtains the liquid after the gas is cooled from the cooling module, and sends the liquid to the reactor through the outlet end of the external circulation system. module.
  • the cooling module includes a gas buffer tank connected to the inlet end, and the gas buffer tank is pressurized by a compressor and arranged in communication with the cooler.
  • the liquid transfer module includes a liquid buffer tank connected to the cooling module, and the liquid buffer tank is pressurized by a circulating pump and communicated with the outlet end.
  • the gas component and the liquid component of the present application are respectively provided with a compressor and a circulating pump for pressurization, so that two-stage pressurization can be performed. transfer effect.
  • the outlet end further includes a spray mechanism.
  • the spray mechanism includes a spray pipe connected to the outlet end, and a plurality of spray heads are arranged on the spray pipe.
  • the spray head is located in the gas-phase space and is disposed toward the solid-liquid space.
  • the method of spraying is used to re-introduce the liquid, so as to increase the disturbance of the solid-liquid space, and also have certain functions of homogenization and stirring.
  • a pressure relief valve is provided between the inlet end and the external circulation system; a feed valve is provided between the outlet end and the external circulation system.
  • the inlet end of the external circulation system is set at the top of the reactor.
  • the reactor is a vertical reactor or a horizontal reactor
  • a stirrer is arranged in the reactor
  • a temperature regulating jacket is arranged outside the reactor
  • a temperature regulating coil is arranged in the reactor.
  • This application is used to prepare hydroxypropyl methylcellulose, hydroxyethyl methylcellulose and other substances from cellulose.
  • the liquid in the solid-liquid space is heated and vaporized, and then enters the
  • the gas phase space is then circulated into the reactor through the external circulation system, so that the pressure in the reactor can be reduced, the overall safety performance can be guaranteed, and the pressure resistance and sealing performance of the reactor can be reduced.
  • the overall investment in the equipment is small, and the liquid continues to pass through the external
  • the circulation system is returned to the reactor, so that the reaction liquid in the reactor is always in excess, the reaction speed is fast, and the production efficiency is high;
  • the parts of the gas component and the liquid component of this application are respectively equipped with compressors and circulating pumps for pressurization, so that two-stage pressurization can be performed, and the transmission pressure of the liquid can be ensured while accelerating the gas liquefaction. , to ensure the transmission effect;
  • the application adopts the method of spraying to re-introduce the liquid to increase the disturbance of the solid-liquid space, and also has a certain effect of homogenization and stirring.
  • FIG. 1 is a schematic diagram of a device for preparing modified cellulose provided by an embodiment of the application
  • FIG. 2 is a schematic diagram of a cooling module provided by an embodiment of the present application.
  • FIG. 3 is a schematic diagram of a liquid delivery module provided by an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a reactor part provided in an embodiment of the present application.
  • first and second are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined as “first” or “second” may expressly or implicitly include one or more of that feature.
  • plurality means two or more, unless otherwise expressly and specifically defined.
  • the terms “installed”, “connected”, “connected”, “fixed” and other terms should be understood in a broad sense, for example, it may be a fixed connection or a detachable connection , or integrated; it can be a mechanical connection, an electrical connection, or a communication; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the internal connection of the two elements or the interaction between the two elements. .
  • installed may be a fixed connection or a detachable connection , or integrated; it can be a mechanical connection, an electrical connection, or a communication; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the internal connection of the two elements or the interaction between the two elements.
  • a first feature "on” or “under” a second feature may be in direct contact with the first and second features, or the first and second features indirectly through an intermediary touch.
  • description with reference to the terms “one embodiment,” “some embodiments,” “example,” “specific example,” or “some examples”, etc. mean specific features described in connection with the embodiment or example , structure, material or feature is included in at least one embodiment or example of the present application.
  • schematic representations of the above terms are not necessarily directed to the same embodiment or example.
  • the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
  • a method and device for preparing modified cellulose including a reaction kettle 1, and the reaction kettle 1 is provided with a solid-liquid space 2 for reaction, and a In the gas-phase space 3 that accommodates the gas overflowing from the solid-liquid space 2, an external circulation system is provided outside the reaction kettle 1, and the inlet end 5 of the external circulation system is communicated with the gas-phase space 3 in the reaction kettle 1.
  • the outlet end 6 is arranged deep into the reactor 1 .
  • the external circulation system includes a cooling module 7 for cooling the gas overflowing from the gas phase space 3 and a liquid transfer module for obtaining the liquid after gas cooling from the cooling module 7 and sending the liquid to the reactor 1 through the outlet end 6 of the external circulation system. 8.
  • the cooling module 7 includes a gas buffer tank 9 connected to the inlet end 5 , and the gas buffer tank 9 is pressurized by a compressor 10 and communicated with the cooler 11 .
  • the liquid transfer module 8 includes a liquid buffer tank 12 connected to the cooling module 7 , and the liquid buffer tank 12 is pressurized by a circulating pump 13 and communicated with the outlet end 6 .
  • the outlet end 6 also includes a spray mechanism.
  • the spray mechanism includes a spray pipe 14 connected to the outlet end 6 , and a plurality of spray heads 15 are arranged on the spray pipe 14 .
  • the shower head 15 is located in the gas phase space 3 and is disposed toward the solid-liquid space 2 .
  • a pressure relief valve 16 is arranged between the inlet end 5 and the external circulation system; a feed valve 17 is arranged between the outlet end 6 and the outer circulation system.
  • the inlet end 5 of the external circulation system is arranged at the top of the reactor 1 .
  • the reactor 1 is a vertical reactor or a horizontal reactor, and a stirrer is provided in the reactor 1, and a temperature regulating jacket is provided outside the reactor 1 or a temperature regulating coil is provided in the reactor 1 (not in the reactor 1). shown in the figure).
  • the feed valve 17 and the pressure relief valve 16 are opened and adjusted according to the pressure and temperature in the reactor 1 to control the pressure and temperature in the reactor 1 in the etherification reaction stage, so that the reaction is carried out at a lower pressure, generally at 0.2 ⁇ 1.0MPa.
  • the synthetic reaction of modified cellulose can be carried out by means of but not limited to the equipment of the first embodiment, and specifically includes the following steps:
  • Comparative example 6 adopts the vertical reaction kettle of 15m , put into the mixed solvent of toluene, isopropanol and water in the reaction kettle, then add caustic soda, and carry out causticization. Then, the cellulose ether powder was added to carry out the reaction.
  • Comparative Example 5 was carried out in a closed reactor equipped with a condenser, without an external circulation system for the reaction liquid.
  • Example 1 and Example 3 prepared hydroxypropyl methylcellulose by the method described in this application;
  • Example 2 prepared hydroxyethyl methylcellulose;
  • Example 4 prepared hydroxypropyl methylcellulose Hydroxyethyl methyl cellulose;
  • Comparative example 5 prepared hydroxypropyl methyl cellulose by traditional gas-solid process;
  • Comparative example 6 prepared hydroxypropyl methyl cellulose by slurry process, all of which belong to modified fibers white.
  • Embodiments 1-4 were reacted by the method described in this application, and Comparative Example 5 was reacted by a traditional gas-solid method, without the participation of inert organic solvents such as toluene and isopropanol. It can be seen from Table 2 that the reaction pressure of Examples 1-4 is lower than that of Comparative Example 5. That is, the method described in this application has a lower reaction pressure than the traditional gas-solid method.
  • Examples 1-4 were reacted using the methods described in this application, and Comparative Example 6 was reacted using a slurry process.
  • Table 1 using the reaction kettle of the same volume, the feeding amount of Example 1-4 is higher than that of Comparative Example 6; as can be seen from Table 3, the output of Example 1-4 is higher than that of Comparative Example 6. That is, the method described in this application has a larger charge than the slurry method.
  • Example 1 was reacted using the method described in this application, and Comparative Example 6 was reacted using a slurry process. It can be seen from Table 2 that under the same reaction temperature, the reaction time of Example 1 is shorter than that of Comparative Example 6. That is, the method described in this application has a shorter reaction time than the slurry method.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

一种制备改性纤维素的方法及装置，包括反应釜，反应釜内设有用于反应的固液空间，和用于容纳从固液空间内溢出的气体的气相空间，在反应釜外设有一外循环系统，外循环系统的入口端与反应釜内的气相空间连通设置，外循环系统的出口端深入到反应釜内设置。本申请用于纤维素制备羟丙基甲基纤维素、羟乙基甲基纤维素等物质，在纤维素醚化反应进行时，在固液空间内的液体受热气化，先进入到气相空间，然后再通过外循环系统循环进入到反应釜内，使得可以降低釜内压力，保证整体的安全性能，降低反应釜的耐压性能和密封性能，同时液体持续经过外循环系统回到反应釜内，使反应釜内反应液始终处于过剩状态，反应速度快，生产效率高。

Description

一种制备改性纤维素的方法及装置 技术领域
本申请涉及一种制备改性纤维素的方法及装置。
本申请要求于2020年12月30日提交中国专利局、申请号为202011617085.X、发明名称为"一种制备改性纤维素的方法及装置"的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
背景技术
羟丙基甲基纤维素(HPMC)和羟乙基甲基纤维素(HEMC)均属非离子型纤维素醚类，易融入水，具有良好的增稠、悬浮、分散、乳化、粘合、成膜、保水和胶体保护等特性，已被广泛应用在涂料、建筑、医药、食品、纺织、造纸以及高分子聚合反应等领域。
纤维素醚反应釜分为卧式反应釜或立式反应釜，可单独作为反应装置使用，或搭配冷却器作为反应装置使用。
单独使用的反应釜适用于淤浆法工艺，醚化剂溶解在惰性有机溶剂中，反应压力一般较低，在0.6MPa以下。但此种工艺反应釜投料量小，反应时间长，生产效率低；惰性有机溶剂需回收再利用，污染大，成本高。
搭配冷却器使用的反应釜适用于气固法工艺，反应釜内无惰性有机溶剂，大量醚化剂和低沸点副产物在反应釜和冷却器内重复气化-冷凝过程，反应压力一般较高，可达2.2-2.35MPa，对反应设备的耐压性能和密封性能有较高要求。
发明内容
为了解决上述问题，本申请实施例提供了一种制备改性纤维素的方法，包括将纤维素进行碱化反应和醚化反应，得到改性纤维素的过程，将碱化纤维素置于循环流动的反应液中，反应液以气态形式离开碱化纤维素，然后以液态形式返回到碱化 纤维素中；反应液为氯甲烷、环氧烷烃和二甲醚。本申请生产过程中无甲苯和异丙醇等惰性有机溶剂参与，无需惰性有机溶剂回收工序，生产工艺简化，污染小，成本低；投料量大，生产效率高。反应液在反应过程中气化后迅速离开反应釜，从而降低反应氛围的压力，安全性能高。
在一实施例中，醚化反应的反应条件为表压0.2-1.0MPa，反应时间1.5-6h，反应温度50-90℃。
在一优选的实施例中，醚化反应的反应条件为表压0.4-0.6MPa。
在一些实施例中，反应液中的各个物质的质量份数为：环氧烷烃：13-65份；氯甲烷：80-140份；二甲醚：60-80份。
在一些实施例中，环氧烷烃为环氧乙烷和/或环氧丙烷。
在一些实施例中，液碱浓度为40-60wt％，纤维素与液碱的质量比为1：0.7-1.7。
另一方面，在一实施例中，本申请还公开了一种制备改性纤维素的装置，包括反应釜，反应釜内设有用于反应的固液空间，和用于容纳从固液空间内溢出的气体的气相空间，在反应釜外设有一外循环系统，外循环系统的入口端与反应釜内的气相空间连通设置，外循环系统的出口端深入到反应釜内设置。本申请用于纤维素制备羟丙基甲基纤维素、羟乙基甲基纤维素等物质，在纤维素醚化反应进行时，在固液空间内的液体受热气化，先进入到气相空间，然后再通过外循环系统循环进入到反应釜内，使得可以降低釜内压力，保证整体的安全性能，降低反应釜的耐压性能和密封性能，设备整体投资小，同时液体持续经过外循环系统回到反应釜内，使反应釜内反应液始终处于过剩状态，反应速度快，生产效率高。
在一实施例中，外循环系统包括用于冷却从气相空间溢出气体的冷却模块和从冷却模块得到气体冷却之后的液体、并将液体通过外循环系统的出口端送入到反应釜的液体传送模块。
在一些实施例中，冷却模块包括与入口端相连的气体缓冲罐，气体缓冲罐通过一压缩机加压后与冷却器连通设置。
在一实施例中，液体传送模块包括与冷却模块相连的液体缓冲罐，液体缓冲罐通过一循环泵加压后与出口端连通设置。本申请的气体组份和液体组份的部分分别设置了用于加压的压缩机、循环泵，从而可以进行两级加压，在加快气体液化的同时，还能保证液体的传输压力，保证传输效果。
在一实施例中，出口端还包括一喷淋机构。
在一实施例中，喷淋机构包括与出口端相连的喷淋管，在喷淋管上设有若干喷头。
在一实施例中，喷头处于气相空间内并朝向固液空间设置。本申请采用喷淋的方式进行液体的重新引入，加大固液空间的扰动，也有一定的均质和进行搅拌的作用。
在一实施例中，入口端和外循环系统之间设有一泄压阀；出口端和外循环系统之间设有一进料阀。
在一实施例中，外循环系统的入口端设置在反应釜的顶部。
在一实施例中，反应釜为立式反应釜或卧式反应釜，在反应釜内设置有搅拌器，在反应釜外设有调温夹套或在反应釜内设有调温盘管。
本申请能够带来如下有益效果：
1、本申请生产过程中无甲苯和异丙醇等惰性有机溶剂参与，无需惰性有机溶剂回收工序，生产工艺简化，污染小，成本低；投料量大，生产效率高。反应液在反应过程中气化后迅速离开反应釜，从而降低反应氛围的压力，安全性能高；
2、本申请用于纤维素制备羟丙基甲基纤维素、羟乙基甲基纤维素等物质，在纤维素醚化反应进行时，在固液空间内的液体受热气化，先进入到气相空间，然后再 通过外循环系统循环进入到反应釜内，使得可以降低釜内压力，保证整体的安全性能，降低反应釜的耐压性能和密封性能，设备整体投资小，同时液体持续经过外循环系统回到反应釜内，使反应釜内反应液始终处于过剩状态，反应速度快，生产效率高；
3、本申请的气体组份和液体组份的部分分别设置了用于加压的压缩机、循环泵，从而可以进行两级加压，在加快气体液化的同时，还能保证液体的传输压力，保证传输效果；
4、本申请采用喷淋的方式进行液体的重新引入，加大固液空间的扰动，也有一定的均质和搅拌的作用。
附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本申请一实施例提供的制备改性纤维素的装置的示意图；
图2为本申请一实施例提供的冷却模块的示意图；
图3为本申请一实施例提供的液体传送模块的示意图；
图4为本申请一实施例提供的反应釜部分的示意图。
实施方式
为能清楚说明本方案的技术特点，下面通过具体实施方式，并结合其附图，对本申请进行详细阐述。
如图中所示，为了更清楚的阐释本申请的整体构思，下面结合说明书附图以示例的方式进行详细说明。
另外，在本申请的描述中，需要理解的是，术语“中心”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“轴向”、“径向”、“周向” 等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
本说明书中的各个实施例均采用递进的方式描述，各个实施例之间相同相似的部分互相参见即可，每个实施例重点说明的都是与其他实施例的不同之处。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
在本申请中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接，还可以是通信；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本申请中的具体含义。
在本申请中，除非另有明确的规定和限定，第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触，或第一和第二特征通过中间媒介间接接触。在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。
在第一个实施例中，如图1-4所示，提供一种制备改性纤维素的方法及装置，包 括反应釜1，反应釜1内设有用于反应的固液空间2，和用于容纳从固液空间2内溢出的气体的气相空间3，在反应釜1外设有一外循环系统，外循环系统的入口端5与反应釜1内的气相空间3连通设置，外循环系统的出口端6深入到反应釜1内设置。外循环系统包括用于冷却从气相空间3溢出气体的冷却模块7和从冷却模块7得到气体冷却之后的液体、并将液体通过外循环系统的出口端6送入到反应釜1的液体传送模块8。冷却模块7包括与入口端5相连的气体缓冲罐9，气体缓冲罐9通过一压缩机10加压后与冷却器11连通设置。液体传送模块8包括与冷却模块7相连的液体缓冲罐12，液体缓冲罐12通过一循环泵13加压后与出口端6连通设置。出口端6还包括一喷淋机构。喷淋机构包括与出口端6相连的喷淋管14，在喷淋管14上设有若干喷头15。喷头15处于气相空间3内并朝向固液空间2设置。入口端5和外循环系统之间设有一泄压阀16；出口端6和外循环系统之间设有一进料阀17。外循环系统的入口端5设置在反应釜1的顶部。反应釜1为立式反应釜或卧式反应釜，在反应釜1内设置有搅拌器，在反应釜1外设有调温夹套或在反应釜1内设有调温盘管(未在图中示出)。
使用时，向反应釜1内加入纤维素粉末和液碱，进行碱化反应；碱化反应结束后再向反应釜1内加入氯甲烷、二甲醚、环氧乙烷或环氧丙烷，进行升温。待反应釜1内压力和温度上升至设定值，打开泄压阀，反应釜1内液体气化后持续进入气体缓冲罐9内，经压缩机10加压，经冷却器11冷凝液化后进入液体缓冲罐12内。液体缓冲罐12内的液体经循环泵13持续通过进料阀17的压力调节，送回到反应釜1内进行醚化反应。在使用过程中，进料阀17和泄压阀16根据反应釜1内压力和温度开启和调节，控制醚化反应阶段反应釜1内压力和温度，使反应在较低压力下进行，一般在0.2～1.0MPa。
在第二个实施例中，可以借助但是不限于第一个实施例的设备进行改性纤维素 的合成反应，具体包括如下步骤：
S1：纤维素碱化：
采用15m 3的卧式反应釜，在反应釜内放入纤维素粉末作为原料纤维素，然后再加入液碱，进行反应，具体的原料含量如表1所示；
表1：
Figure PCTCN2021139048-appb-000001
对比例6采用15m 3的立式反应釜，在反应釜内放入甲苯、异丙醇和水的混合溶剂，之后加入片碱，进行化碱。之后加入纤维素醚粉末，进行反应。
S2：醚化反应：
再向卧式反应釜加入氯甲烷、环氧烷烃和二甲醚，然后向反应釜升温，至反应釜内压力和温度到达预定值，开打泄压阀，启动压缩机、冷凝器降温水和反应液循环泵，进行反应液外循环，计时预定时间后结束反应，具体条件如表2所示；
表2：
Figure PCTCN2021139048-appb-000002
对比例5在配有冷凝器的密闭的反应釜内进行，无反应液外循环系统。
对比例6未加入二甲醚。
S3：S2的反应釜中粗物料经洗涤纯化和干燥粉碎，得到改性纤维素成品；
S4：对改性纤维素成品进行参数表征，具体参数如表3所示。
表3：
Figure PCTCN2021139048-appb-000003
由表3可见，实施例1和实施例3采用本申请中描述的方法制得了羟丙基甲基纤维素；实施例2制得了羟乙基甲基纤维素；实施例4制得了羟丙基羟乙基甲基纤维素；对比例5采用传统气固法工艺制得了羟丙基甲基纤维素；对比例6采用淤浆法工艺制得了羟丙基甲基纤维素，均属于改性纤维素。
实施例1-4采用本申请中描述的方法进行反应，对比例5采用传统气固法工艺进行反应，均无甲苯、异丙醇等惰性有机溶剂参与。由表2可见，实施例1-4反应压力比对比例5低。即本申请中描述的方法比传统气固法反应压力低。
实施例1-4采用本申请中描述的方法进行反应，对比例6采用淤浆法工艺进行反应。由表1可见，采用同样容积的反应釜，实施例1-4投料量比对比例6高；由表3可见，实施例1-4产量比对比例6高。即本申请中描述的方法比淤浆法投料量大。
实施例1采用本申请中描述的方法进行反应，对比例6采用淤浆法工艺进行反应。由表2可见，在同样反应温度下，实施例1反应时间比对比例6短。即本申请中描述的方法比淤浆法反应时间短。
本说明书中的各个实施例均采用递进的方式描述，各个实施例之间相同相似的部分互相参见即可，每个实施例重点说明的都是与其他实施例的不同之处。尤其，对于系统实施例而言，由于其基本相似于方法实施例，所以描述的比较简单，相关之处参见方法实施例的部分说明即可。
以上仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。

Claims (10)

  1. 一种制备改性纤维素的方法，包括将纤维素进行碱化反应和醚化反应，得到改性纤维素的过程，其特征在于：将碱化纤维素置于循环流动的反应液中，所述反应液以气态形式离开碱化纤维素，然后以液态形式返回到碱化纤维素中；所述反应液为氯甲烷、环氧烷烃和二甲醚。
  2. 根据权利要求1所述的一种制备改性纤维素的方法，其特征在于：所述醚化反应的反应条件为表压0.2-1.0MPa，反应时间1.5-6h，反应温度50-90℃。
  3. 根据权利要求2所述的一种制备改性纤维素的方法，其特征在于：所述醚化反应的反应条件为表压0.4-0.6MPa。
  4. 根据权利要求1所述的一种制备改性纤维素的方法，其特征在于：所述反应液中的各个物质的质量份数为：环氧烷烃：13-65份；氯甲烷：80-140份；二甲醚：60-80份。
  5. 根据权利要求1所述的一种制备改性纤维素的方法，其特征在于：所述环氧烷烃为环氧乙烷和/或环氧丙烷。
  6. 根据权利要求1所述的一种制备改性纤维素的方法，其特征在于：所述液碱浓度为40-60wt％，所述纤维素与液碱的质量比为1：0.7-1.7。
  7. 一种制备改性纤维素的装置，其特征在于：包括反应釜，所述反应釜内设有用于反应的固液空间，和用于容纳从固液空间内溢出的气体的气相空间，在反应釜外设有一外循环系统，所述外循环系统的入口端与反应釜内的气相空间连通设置，所述外循环系统的出口端深入到反应釜内设置。
  8. 根据权利要求7所述的一种制备改性纤维素的装置，其特征在于：所述外循环系统包括用于冷却从气相空间溢出气体的冷却模块和从冷却模块得到气体冷却之后的液体、并将液体通过外循环系统的出口端送入到反应釜的液体传送模块；所述冷却模块包括与入口端相连的气体缓冲罐，气体缓冲罐通过一压缩机加压后与冷却 器连通设置。
  9. 根据权利要求8所述的一种制备改性纤维素的装置，其特征在于：所述液体传送模块包括与冷却模块相连的液体缓冲罐，液体缓冲罐通过一循环泵加压后与出口端连通设置；所述出口端还包括一喷淋机构；所述喷淋机构包括与出口端相连的喷淋管，在喷淋管上设有若干喷头；所述喷头处于气相空间内并朝向固液空间设置。
  10. 根据权利要求7所述的一种制备改性纤维素的装置，其特征在于：所述入口端和外循环系统之间设有一泄压阀；所述出口端和外循环系统之间设有一进料阀；所述外循环系统的入口端设置在反应釜的顶部；所述反应釜为立式反应釜或卧式反应釜，在反应釜内设置有搅拌器，在反应釜外设有调温夹套或在反应釜内设有调温盘管。
PCT/CN2021/139048 2020-12-30 2021-12-17 一种制备改性纤维素的方法及装置 WO2022143214A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011617085.XA CN112592411B (zh) 2020-12-30 2020-12-30 一种制备改性纤维素的方法及装置
CN202011617085.X 2020-12-30

Publications (1)

Publication Number Publication Date
WO2022143214A1 true WO2022143214A1 (zh) 2022-07-07

Family

ID=75206355

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/139048 WO2022143214A1 (zh) 2020-12-30 2021-12-17 一种制备改性纤维素的方法及装置

Country Status (2)

Country Link
CN (1) CN112592411B (zh)
WO (1) WO2022143214A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112592411B (zh) * 2020-12-30 2024-04-19 山东一滕新材料股份有限公司 一种制备改性纤维素的方法及装置

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH33571A (fr) * 1905-02-27 1905-12-31 Maurice Denis Installation pour le filage des collodions et la récupération des dissolvants de la nitro-cellulose et de la cellulose
GB355382A (en) * 1929-06-12 1931-08-27 Us Ind Alcohol Co Manufacture of cellulose derivatives
GB1166060A (en) * 1965-12-30 1969-10-01 Kalle Ag Process for the Manufacture of Cellulose Ethers
CN102181070A (zh) * 2011-03-25 2011-09-14 泰安赛露纤维素醚科技有限公司 纤维素醚生产溶剂循环蒸发工艺
CN204607904U (zh) * 2015-03-24 2015-09-02 山东一滕新材料股份有限公司 一种纤维素醚生产中醚化剂回收再利用的系统
CN107098982A (zh) * 2017-05-03 2017-08-29 浙江中维药业股份有限公司 羟丙甲纤维素的生产方法
CN111214844A (zh) * 2020-01-17 2020-06-02 山东赫达股份有限公司 纤维素混合醚的清洁生产系统及生产工艺
CN112592411A (zh) * 2020-12-30 2021-04-02 山东一滕新材料股份有限公司 一种制备改性纤维素的方法及装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106986945A (zh) * 2017-03-24 2017-07-28 山东滕新材料股份有限公司 速溶纤维素醚的制备方法
CN109336984A (zh) * 2018-09-18 2019-02-15 宁夏宸宇精细化学品有限责任公司 高粘度羟丙基甲基纤维素及其制备方法
CN210215211U (zh) * 2019-05-30 2020-03-31 山东一滕新材料股份有限公司 一种制备羟乙基纤维素的装置
CN110804103A (zh) * 2019-12-24 2020-02-18 山东赫达股份有限公司 纤维素混合醚的气固法生产工艺

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH33571A (fr) * 1905-02-27 1905-12-31 Maurice Denis Installation pour le filage des collodions et la récupération des dissolvants de la nitro-cellulose et de la cellulose
GB355382A (en) * 1929-06-12 1931-08-27 Us Ind Alcohol Co Manufacture of cellulose derivatives
GB1166060A (en) * 1965-12-30 1969-10-01 Kalle Ag Process for the Manufacture of Cellulose Ethers
CN102181070A (zh) * 2011-03-25 2011-09-14 泰安赛露纤维素醚科技有限公司 纤维素醚生产溶剂循环蒸发工艺
CN204607904U (zh) * 2015-03-24 2015-09-02 山东一滕新材料股份有限公司 一种纤维素醚生产中醚化剂回收再利用的系统
CN107098982A (zh) * 2017-05-03 2017-08-29 浙江中维药业股份有限公司 羟丙甲纤维素的生产方法
CN111214844A (zh) * 2020-01-17 2020-06-02 山东赫达股份有限公司 纤维素混合醚的清洁生产系统及生产工艺
CN112592411A (zh) * 2020-12-30 2021-04-02 山东一滕新材料股份有限公司 一种制备改性纤维素的方法及装置

Also Published As

Publication number Publication date
CN112592411A (zh) 2021-04-02
CN112592411B (zh) 2024-04-19

Similar Documents

Publication Publication Date Title
WO2022143214A1 (zh) 一种制备改性纤维素的方法及装置
WO2022135443A1 (zh) 一种有机硅助剂的制备方法
CN102276479A (zh) 液相连续加氢法生产对苯二胺的方法及装置
CN214735491U (zh) 一种制备改性纤维素的反应装置
CN114105735A (zh) 一种格尔伯特醇醚的制备方法及其生产装置
CN104557536A (zh) 一种丁二酸单甲酯的制备方法
CN111979820A (zh) 一种通过超临界-高压均质技术制备秸秆纳米纤维素分散液的方法
CN107573427A (zh) 一种羟丙基麦芽糊精的制备方法
CN109575029B (zh) 一种制备美罗培南的连续反应装置及其制备方法
TW555739B (en) Process for the production of polyisocyanates having a biuret structure
CN115626957A (zh) 一种骨架缓释用羟丙甲纤维素的生产方法
CN113548996A (zh) 一种n-乙基吡咯烷酮的合成工艺
CN115569613A (zh) 一种高抗冲击型pvc树脂生产装置及方法
WO2018209735A1 (zh) 一种丙烯酸酯的低温液相制备方法
CN107163153A (zh) 一种高取代度羧甲基淀粉的滚筒干燥制备方法
CN205838890U (zh) 一种高反应选择性n‑乙基‑n‑氰乙基苯胺的生产设备
CN107540750B (zh) 一种羧甲基麦芽糊精的制备方法
CN209519765U (zh) 一种聚甲醛二甲醚制备反应装置
CN104174344B (zh) 一种制备聚甲氧基二甲醚的反应装置和方法
CN114940666A (zh) 一种n-甲基吗啉氧化物水溶液高产率合成方法
CN107964048A (zh) 一种涂料用疏水缔合羟乙基纤维素
CN111072521A (zh) 一种连续化生产盐酸二甲双胍的工艺设备系统
CN210765079U (zh) 一种制备2,2-双(4-羟苯基)六氟丙烷的设备
CN218609110U (zh) 一种溴化sbs阻燃母粒生产用上料装置
CN218422779U (zh) 一种甲基封端聚醚生产装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21913955

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21913955

Country of ref document: EP

Kind code of ref document: A1