技术领域technical field
本发明属于松香深加工技术领域，涉及一种跨临界CO2催化酯化-分离耦合制备松香酯的方法及装置。The invention belongs to the technical field of rosin deep processing, and relates to a method and a device for preparing rosin ester through transcriticalCO2 catalytic esterification-separation coupling.
背景技术Background technique
松香酯是松香深加工中最重要的品种，占松香深加工产品的60％以上。由于松香树脂酸具有三环菲骨架结构，使羧基空间位阻大，导致酯化反应活化能高，而且松香反应体系的黏度又大，造成反应物间的相际传递困难，因此需要在ZnO等酸性金属氧化物催化剂和高温条件下，松香树脂酸才能进行酯化反应。然而在高温条件下，松香树脂酸容易发生脱羧副反应，导致松香酯产品的酯化反应得率和产品质量降低。为了提高松香酯的反应速度和产品质量，在松香酯的浅色化和无气味方面做了许多研发工作。Rosin ester is the most important species in rosin deep processing, accounting for more than 60% of rosin deep processing products. Because rosin resin acid has a three-ring phenanthrene skeleton structure, the steric hindrance of the carboxyl group is large, resulting in high activation energy of the esterification reaction, and the viscosity of the rosin reaction system is high, resulting in difficulty in interphase transfer between reactants. The esterification reaction of rosin resin acid can only be carried out under the conditions of acidic metal oxide catalyst and high temperature. However, under high temperature conditions, the rosin resin acid is prone to decarboxylation side reactions, resulting in a reduction in the esterification yield and product quality of rosin ester products. In order to improve the reaction speed and product quality of rosin ester, a lot of research and development work has been done on the light color and odorless of rosin ester.
现今技术中，采用催化剂对松香深加工后制备成松香酯的技术中，催化剂大多使用金属催化剂对松香进行酯化，从而得到松香酯，但是使用金属催化剂进行催化会使得金属离子对松香酯造成污染，如果使用被金属离子污染后的松香酯用作食品制作，人体使用后会有不好的影响。而且，现今技术中对松香酯的制备因为使用了金属催化剂，有时候甚至使用贵金属催化剂进行催化反应生产，造成生产成本较高等问题，使得在生产松香酯的过程中利润不高。In the current technology, in the technology of preparing rosin esters after deep processing of rosin with catalysts, most of the catalysts use metal catalysts to esterify rosin to obtain rosin esters, but the use of metal catalysts for catalysis will cause metal ions to pollute rosin esters. If the rosin ester contaminated by metal ions is used for food production, it will have adverse effects on the human body after use. Moreover, the preparation of rosin esters in the current technology is due to the use of metal catalysts, sometimes even noble metal catalysts for catalytic reaction production, resulting in problems such as higher production costs, making the profit in the process of producing rosin esters not high.
发明内容Contents of the invention
本发明为解决上述技术问题，发明一种跨临界CO2催化酯化-分离耦合制备松香酯的方法及装置，旨在提供一种成本较低，松香酯质量佳的制备方法。In order to solve the above-mentioned technical problems, the present invention invents a method and device for preparing rosin ester through transcriticalCO2 catalyzed esterification-separation coupling, aiming to provide a preparation method with low cost and good quality of rosin ester.
为实现本发明目的，本发明技术方案如下：For realizing the object of the present invention, the technical scheme of the present invention is as follows:
跨临界CO2催化酯化-分离耦合制备松香酯的方法，包含以下操作步骤：TranscriticalCO Catalyzed esterification-separation coupling prepares the method for rosin ester, comprises the following steps:
(1)将醇类化合物、松香与溶剂混合，溶解；(1) Alcohol compounds, rosin and solvent are mixed and dissolved;
(2)将步骤(1)中溶解后的物质放入酯化反应器中，通入0.01～10.0MPa 的CO2进行酯化反应，酯化反应温度为150～300℃；(2) Put the dissolved substance in the step (1) into the esterification reactor, and introduce 0.01-10.0MPa of CO2 to carry out the esterification reaction, and the esterification reaction temperature is 150-300°C;
(3)对酯化反应过程中的气相进行采出，气相通过膨胀机进入气液分离器，分离后CO2以及新补充的CO2通过透平压缩机回到酯化反应器内；(3) The gas phase in the esterification reaction process is extracted, and the gas phase enters the gas-liquid separator through an expander, andCO after separation and newly supplementedCO return in the esterification reactor through a turbo compressor;
(4)酯化反应器内反应1.0～8.0h减压后，所得产品从酯化反应器内取出即可。(4) After 1.0-8.0 hours of reaction in the esterification reactor and decompression, the product obtained can be taken out from the esterification reactor.
优选的是，步骤(1)中按照摩尔比醇类化合物：松香＝1:1～10:1混合，加入原料质量分数为0～50％的溶剂混合。Preferably, in step (1), the alcohol compound: rosin is mixed according to the molar ratio of 1:1-10:1, and the solvent with a mass fraction of raw materials of 0-50% is added for mixing.
优选的是，步骤(2)～(3)中从酯化反应器流出的气相流量为0～12000m3/h、压力为0～10.0MPa、温度为150～300℃；经膨胀机膨胀降压或节流膨胀降压为0～0.5MPa，降温为0℃～50℃，再经透平压缩机加压流回酯化反应器，气体流量为0～10000m3/h，压力为0～10.0MPa，温度为150℃～300℃。Preferably, in steps (2)-(3), the flow rate of the gas phase flowing out of the esterification reactor is 0-12000m3 /h, the pressure is 0-10.0MPa, and the temperature is 150-300°C; Or throttling expansion and depressurization to 0~0.5MPa, cooling to 0℃~50℃, and then pressurized by the turbine compressor to flow back to the esterification reactor, the gas flow rate is 0~10000m3 /h, and the pressure is 0~10.0 MPa, the temperature is 150°C to 300°C.
优选的是，步骤(3)中气液分离器的温度为0～50℃，压力为0.0～0.5MPa，液体流量为0～100m3/h，气体流量为0～10000m3/h。优选的是，所述的溶剂为松节油、碳酸二甲酯、矿物精油、200#溶剂油中的一种。Preferably, the temperature of the gas-liquid separator in step (3) is 0-50°C, the pressure is 0.0-0.5MPa, the liquid flow rate is 0-100m3 /h, and the gas flow rate is 0-10000m3 /h. Preferably, the solvent is one of turpentine, dimethyl carbonate, mineral essential oil, and 200# solvent naphtha.
优选的是，所述的醇类化合物为丙三醇、甲醇、乙醇中的一种。Preferably, the alcohol compound is one of glycerol, methanol and ethanol.
其中，步骤(2)中所述酯化反应过程中的气相含有醇类化合物蒸汽、水蒸气、CO2。Wherein, the gas phase during the esterification reaction in step (2) contains alcohol compound vapor, water vapor and CO2 .
一种催化酯化-分离耦合制备松香酯方法的装置，包括：酯化反应器，其包括：多个加热管，设于酯化反应器内部；以及气体分布器，其包括进气口和多个用于排气的喷头；A device for catalyzing esterification-separation coupled method for preparing rosin esters, comprising: an esterification reactor, which includes: a plurality of heating pipes arranged inside the esterification reactor; and a gas distributor, which includes an air inlet and multiple nozzles for exhaust;
膨胀机，其与所述酯化反应器连接；以及透平压缩机，其与所述膨胀机连接，并通过所述膨胀机驱动所述透平压缩机工作，所述透平压缩机的出气口与所述酯化反应器连接。An expander, which is connected with the esterification reactor; and a turbo compressor, which is connected with the expander, and drives the turbo compressor to work through the expander, and the outlet of the turbo compressor The gas port is connected with the esterification reactor.
优选地，上述技术方案中，所述气体分布器呈“L”型，其底端为圆环管状，在该圆环管上均匀设有多个用于排气的喷头，所述喷头倾斜设置。Preferably, in the above technical solution, the gas distributor is in an "L" shape, and its bottom end is in the shape of a ring tube, and a plurality of nozzles for exhaust are uniformly arranged on the ring tube, and the nozzles are arranged obliquely .
优选地，上述技术方案中，所述加热管为多个，呈平行均布在所述酯化反应器内部；所述气体分布器有多个，所述多个气体分布器相互连通，所述每个气体分布器设在所述加热管之间。Preferably, in the above technical solution, there are multiple heating pipes, which are distributed in parallel and evenly inside the esterification reactor; there are multiple gas distributors, and the multiple gas distributors communicate with each other. Each gas distributor is provided between the heating tubes.
优选地，上述技术方案中，所述用于，还包括：溶解釜，其与所述酯化反应器内部相连；所述气体分布器有多个，所述多个气体分布器相互连通， 所述每个气体分布器设在所述加热管之间。Preferably, in the above technical solution, the use further includes: a dissolution tank, which is connected to the inside of the esterification reactor; there are multiple gas distributors, and the multiple gas distributors communicate with each other, so Each of the gas distributors is arranged between the heating tubes.
优选地，上述技术方案中，所述用于催化酯化-分离耦合制备松香酯方法的装置，还包括：溶解釜，其与所述酯化反应器连接，用于溶解生产所需的原料；气液分离器，其进气口与所述膨胀机连接，出气口与透平压缩机连接；分离塔，其出料口与所述透平压缩机连接；以及回流泵，其与所述分离塔连接，用于将分离出的液体溶剂送至所述酯化反应器内。Preferably, in the above technical solution, the device for catalyzing the esterification-separation coupled method for preparing rosin ester also includes: a dissolution tank connected to the esterification reactor for dissolving raw materials required for production; A gas-liquid separator, whose air inlet is connected with the expander, and whose gas outlet is connected with the turbocompressor; a separation tower, whose discharge port is connected with the turbocompressor; and a reflux pump, which is connected with the separator The tower is connected to send the separated liquid solvent to the esterification reactor.
本发明方法是把醇类化合物和松香加入熔解釜熔解后压入酯化反应器，通入CO2，使温度与压力到达CO2超/亚临界状态，利用超/亚临界CO2溶解于醇类化合物、松香和酯化反应生成的水中，形成质子酸，然后以所形成的质子酸作为催化剂对醇类化合物与松香催化酯化反应生成松香酯和水。在酯化反应的高温条件下，醇类化合物水蒸气与生成的水蒸汽混合气相物料在一起被循环CO2夹带不断地从酯化反应器内流出，进入膨胀机中，并使膨胀机膨胀做功驱动透平压缩机，以达到膨胀—压缩自循环。由酯化反应器流出混合气相物质，主要是CO2，从超/亚临界状态跃迁为低温低压常态即称为跨临界状态，从超/亚临界状态向低温低压常态跃迁形成压降，从而使得膨胀机膨胀做功。酯化反应器中流出的混合气相物料从膨胀机流经气液分离器进行冷凝与气、液相分离，所得液体为醇类和水溶液；CO2气体作为循环与新补充的CO2经透平压缩机加压后流回酯化反应器。从气液分离器中分离后所得醇类化合物、水混合液体，进入分离塔进行分离，得到的水从分离塔流出，而醇类化合物则进入回流泵中，循环进入酯化反应器中参与反应。由于从酯化反应器流出的混合气相物质含有醇类化合物、CO2和水与溶剂的蒸汽，而加压循环的气体仅为不凝气体CO2，这是因为经膨胀机膨胀降压降温后，醇类化合物、水与溶剂的蒸汽冷凝为液体从气液分离器中分离出来，而用于循环的气体仅剩下不凝气体CO2，可见驱动膨胀机的气体流量大于透平压缩机加压循环气体的流量，亦即是说膨胀机做出的膨胀功大于透平压缩机所需的压缩功，系统所需增加的能量由酯化反应器内酯化放出的反应热和加热盘管供给热能以提高溶剂蒸汽流量。往透平压缩机内通入新补充的CO2气体，膨胀机直接推动透平压缩机加压CO2循环回系统，然后再通入酯化反应器内。The method of the present invention is that the alcohol compound and rosin are added into the melting pot for melting, and then pressed into the esterification reactor, and CO2 is introduced to make the temperature and pressure reach the CO2 super/subcritical state, and the super/subcritical CO2 is dissolved in the alcohol Alcohol compounds, rosin and the water generated by the esterification reaction form protonic acid, and then use the formed protonic acid as a catalyst to catalyze the esterification reaction of alcohol compound and rosin to generate rosin ester and water. Under the high temperature conditions of the esterification reaction, the water vapor of the alcohol compound and the generated water vapor mixed gas phase material are entrained by the circulating CO2 and continuously flow out of the esterification reactor, enter the expander, and make the expander expand to do work Drive the turbo-compressor to achieve expansion-compression self-circulation. The mixed gas phase substances flowing out of the esterification reactor, mainly CO2 , transition from the super/subcritical state to the low temperature and low pressure normal state, which is called the transcritical state. The transition from the super/subcritical state to the low temperature and low pressure normal state forms a pressure drop, so that The expander expands to do work. The mixed gas phase material flowing out of the esterification reactor flows from the expander through the gas-liquid separator for condensation and gas-liquid phase separation, and the obtained liquid is alcohols and aqueous solution; CO2 gas is used as a cycle and the newly supplemented CO2 passes through the turbine After the compressor is pressurized, it flows back to the esterification reactor. After separation from the gas-liquid separator, the mixed liquid of alcohol compound and water enters the separation tower for separation, and the obtained water flows out from the separation tower, while the alcohol compound enters the reflux pump and circulates into the esterification reactor to participate in the reaction . Since the mixed gas phase material flowing out of the esterification reactor contains alcohol compounds, CO2 and steam of water and solvent, and the gas in the pressurized cycle is only non-condensable gas CO2 , the vapors of alcohol compounds, water and solvents are condensed into liquids and separated from the gas-liquid separator, and only non-condensable gas CO2 is left in the gas used for circulation. It can be seen that the gas flow rate driving the expander is greater than that of the turbo compressor. The flow rate of the compressed cycle gas, that is to say, the expansion work done by the expander is greater than the compression work required by the turbo compressor, and the increased energy required by the system comes from the reaction heat released by the esterification in the esterification reactor and the heating coil Heat energy is supplied to increase solvent vapor flow. The newly supplemented CO2 gas is fed into the turbo compressor, and the expander directly pushes the turbo compressor to pressurize the CO2 to circulate back to the system, and then pass into the esterification reactor.
由于醇类化合物与松香的酯化反应是以CO2为催化剂前驱体，既节约了催化剂成本又避免了加入ZnO等金属催化剂对产品的污染，而且酸与醇经酯 化反应生成的水又被CO2夹带不断地流出酯化反应器，从而消除了副产物水累积而引起的反馈抑制作用，打破了羧酸与醇的酯化反应的化学平衡，提高了酯化反应速度和平衡转化率，实现酯化反应-分离耦合的目的；又由于CO2在酯化反应器内不断地循环鼓泡流动，强化了对松香高黏性物的搅拌和热质传递，而且CO2还产生“超空泡”效应，既减省了酯化反应器内的搅拌器安装，又最大限度地减少了松香高黏性物料间的传递阻力和三环菲骨架上羧基的空间位阻，大大地提高了酯化反应器(2)的传热与传质速度和反应效能。况且，CO2还可以产生“同分子”效应，能抑制松香树脂酸脱羧生成CO2的副反应，从而提高了松香酯的反应选择性和收率以及产品质量。Since the esterification reaction of alcohol compounds and rosin usesCO2 as the catalyst precursor, it not only saves the cost of the catalyst but also avoids the pollution of the product by adding metal catalysts such as ZnO, and the water generated by the esterification reaction of acid and alcohol is used again.CO2 entrainment continuously flows out of the esterification reactor, thereby eliminating the feedback inhibition effect caused by the accumulation of by-product water, breaking the chemical balance of the esterification reaction of carboxylic acid and alcohol, improving the speed of esterification reaction and the equilibrium conversion rate, Realize the purpose of esterification reaction-separation coupling; and because CO2 is continuously circulating and bubbling in the esterification reactor, the stirring and heat and mass transfer of the high-viscosity rosin are strengthened, and CO2 also produces "super-empty "bubble" effect, which not only saves the installation of the agitator in the esterification reactor, but also minimizes the transmission resistance between the high-viscosity materials of rosin and the steric hindrance of the carboxyl group on the tricyclic phenanthrene skeleton, greatly improving the esterification rate. The heat transfer and mass transfer rate and reaction performance of chemical reactor (2). Moreover,CO2 can also produce a "same molecule" effect, which can inhibit the side reaction of decarboxylation of rosin resin acid to generateCO2 , thereby improving the reaction selectivity, yield and product quality of rosin ester.
与现有技术相比，本发明的有益效果：Compared with prior art, the beneficial effect of the present invention:
1、以超/亚临界CO2溶解于醇类化合物、松香和酯化反应生成的水中，所形成的质子酸替代ZnO等金属催化剂制备松香酯，避免金属离子对松香酯的污染，特别是制备食品级松香酯产品，本发明方法生产的产品更安全可靠，是一种绿色催化酯化方法和清洁生产过程。1. Dissolve super/subcriticalCO2 in the water generated by alcohol compounds, rosin and esterification reaction, and the formed protonic acid replaces ZnO and other metal catalysts to prepare rosin esters, so as to avoid the pollution of rosin esters by metal ions, especially for the preparation of rosin esters. The food-grade rosin ester product produced by the method of the invention is safer and more reliable, and is a green catalytic esterification method and a clean production process.
2、醇类化合物与松香酯化反应生成的水被CO2不断地夹带出酯化反应器，从而消除了产物累积而引起的反馈抑制作用，打破了醇与酸酯化反应化学平衡，使反应不断地朝着生成松香酯的方向进行，从而提高了酯化反应速度和平衡转化率，实现松香树脂酸与醇的酯化-分离的耦合。2. The water generated by the esterification reaction of alcohol compounds and rosin is continuously carried out of the esterification reactor byCO2 , thus eliminating the feedback inhibition effect caused by product accumulation, breaking the chemical balance between alcohol and esterification reaction, and making the reaction Continuously proceed towards the direction of generating rosin ester, thereby improving the esterification reaction speed and equilibrium conversion rate, and realizing the coupling of esterification-separation of rosin resin acid and alcohol.
3、采用跨临界CO2膨胀—压缩自循环技术，使从跨临界反应器流出的高压CO2和水、醇类化合物以及溶剂的蒸汽经膨胀机膨胀直接推动透平压缩机加压不凝气体CO2循环回系统，减少了热功转换过程：热能→机械能→电能→机械能的有效能损失，提高了热能转换的热功效率。3. Adopt transcritical CO2 expansion-compression self-circulation technology, so that the steam of high-pressure CO2 , water, alcohol compounds and solvents flowing out of the transcritical reactor is expanded by the expander to directly push the turbine compressor to pressurize the non-condensable gas CO2 is recycled back to the system, which reduces the heat work conversion process: thermal energy→mechanical energy→electrical energy→mechanical energy, which improves the heat work efficiency of heat energy conversion.
4、超/亚临界CO2在酯化反应器中不断地循环鼓泡流动搅拌和产生“超空泡”效应，强化了反应器内高黏性物料的传热与传质，既减省了酯化反应器的搅拌器安装又最大限度地减少了高黏性松香物料间的传递阻力和三环菲骨架上羧基的空间位阻，大大提高了酯化反应器的传热与传质和酯化反应效果。4. Super/subcritical CO2 continuously circulates bubbling flow and agitation in the esterification reactor and produces a "super cavitation" effect, which strengthens the heat transfer and mass transfer of high-viscosity materials in the reactor, which saves The installation of the agitator in the esterification reactor minimizes the transfer resistance between the high-viscosity rosin materials and the steric hindrance of the carboxyl groups on the tricyclic phenanthrene skeleton, greatly improving the heat transfer and mass transfer of the esterification reactor and the esterification efficiency. chemical reaction effect.
5、超/亚临界CO2在酯化反应器产生“同分子”效应，抑制松香树脂酸脱羧生成CO2的副反应，从而提高了松香酯的反应选择性和产品质量，降低了生产成本和损耗。5. Super/subcriticalCO2 produces a "same molecule" effect in the esterification reactor, which inhibits the side reaction ofCO2 generated from the decarboxylation of rosin resin acid, thereby improving the reaction selectivity and product quality of rosin esters, reducing production costs and loss.
6、酯化反应器采用超/亚临界CO2进行鼓泡搅拌，不需要安装机械搅拌装 置，更有利于高压设备的制造、操作、维修和防漏。6. The esterification reactor adopts super/subcritical CO2 for bubbling and stirring, and does not need to install a mechanical stirring device, which is more conducive to the manufacture, operation, maintenance and leakage prevention of high-pressure equipment.
附图说明Description of drawings
图1为催化酯化-分离耦合制备松香酯方法流程图，其中1是溶解釜，2是酯化反应器，3是膨胀机，4是气液分离器，5是透平压缩机，6是分离塔，7是回流泵。Fig. 1 is the flow chart of the method for preparing rosin ester by catalytic esterification-separation coupling, wherein 1 is a dissolution tank, 2 is an esterification reactor, 3 is an expander, 4 is a gas-liquid separator, 5 is a turbine compressor, and 6 is Separation tower, 7 is reflux pump.
图2是根据本发明酯化反应器的结构示意图，其中21是进料口，22是出气口，23是出料口，24是加热盘管，25为气体分布器，251是进气口，252是喷头。Fig. 2 is the structural representation of esterification reactor according to the present invention, and wherein 21 is feed inlet, and 22 is gas outlet, and 23 is outlet, and 24 is heating coil, and 25 is gas distributor, and 251 is air inlet, 252 is a shower head.
图3是根据本发明酯化反应器中单个气体分布器的结构示意图。Fig. 3 is a schematic structural view of a single gas distributor in an esterification reactor according to the present invention.
图4是根据本发明酯化反应器中单个气体分布器的俯视图。Fig. 4 is a top view of a single gas distributor in an esterification reactor according to the present invention.
具体实施方式detailed description
以下参照具体实施方式来进一步描述本发明，以令本领域技术人员参照说明书文字能够据以实施，本发明保护范围并不受制于本发明的实施方式。The present invention will be further described below with reference to specific embodiments, so that those skilled in the art can implement according to the text of the description, and the protection scope of the present invention is not limited by the embodiments of the present invention.
实施例1Example 1
如附图1-4所示，用于催化酯化-分离耦合制备松香酯方法的装置，包括：溶解釜1、酯化反应器2、膨胀机3、气液分离器4、透平压缩机5、分离塔6、回流泵7。As shown in accompanying drawing 1-4, be used for the device of catalyzed esterification-separation coupling preparation method of rosin ester, comprise: dissolving kettle 1, esterification reactor 2, expander 3, gas-liquid separator 4, turbine compressor 5. Separation tower 6, reflux pump 7.
溶解釜1的出料口与所述酯化反应器2的进料口连接，溶解釜1用于溶解生产所需的原料。酯化反应器2，呈圆柱形，酯化反应器的上部设有进料口21、出气口22，底部设有出料口23，酯化反应器2包括加热管24，为加热盘管，其设于酯化反应器内部；气体分布器25，其包括进气口251和多个用于排气的喷头252；膨胀机3与所述酯化反应器2的出气口连接。透平压缩机5与所述膨胀机3连接，并通过所述膨胀机3驱动所述透平压缩机5工作，所述透平压缩机5的出气口与所述酯化反应器2连接。气液分离器4与所述膨胀机3连接，用于分离反应后产生的混合气相，分离出气体和液体。分离塔6的进气口与所述气液分离器4连接，用于去除需要去除的气体；回流泵7与分离塔4连接，用于将分离出的液体溶剂送至所述酯化反应器2内。The discharge port of the dissolution kettle 1 is connected with the feed port of the esterification reactor 2, and the dissolution kettle 1 is used for dissolving raw materials required for production. The esterification reactor 2 is cylindrical, and the top of the esterification reactor is provided with a feed inlet 21, a gas outlet 22, and the bottom is provided with a discharge outlet 23, and the esterification reactor 2 includes a heating pipe 24, which is a heating coil. It is arranged inside the esterification reactor; the gas distributor 25 includes an air inlet 251 and a plurality of nozzles 252 for exhaust; the expander 3 is connected to the gas outlet of the esterification reactor 2 . The turbocompressor 5 is connected with the expander 3, and the turbocompressor 5 is driven to work by the expander 3, and the gas outlet of the turbocompressor 5 is connected with the esterification reactor 2. The gas-liquid separator 4 is connected with the expander 3, and is used for separating the mixed gas phase generated after the reaction, and separating gas and liquid. The gas inlet of separation tower 6 is connected with described gas-liquid separator 4, is used for removing the gas that needs to be removed; Reflux pump 7 is connected with separation tower 4, is used for sending the separated liquid solvent to described esterification reactor 2 within.
优选地，所述气体分布器25呈“L”型，其底端为圆环管状，在该圆环 管上均匀设有多个用于排气的喷头252，所述喷头为“L”型，成同一方向倾斜设置。在呈环状的管上均布有多个排气喷头，使气体排放更为均匀，使得至于酯化反应器内的物料与气体充分接触，加快反应速率。呈倾斜设置的喷头喷出的气体往同一方向倾斜喷出气体，使气泡呈旋转状在酯化反应器2内运动，使得反应的物料与气体充分接触，加快反应速度。Preferably, the gas distributor 25 is in an "L" shape, and its bottom end is in the shape of a circular tube, and a plurality of nozzles 252 for exhaust are uniformly arranged on the circular tube, and the nozzles are in an "L" shape , inclined in the same direction. Multiple exhaust nozzles are evenly distributed on the ring-shaped pipe to make the gas discharge more uniform, so that the materials in the esterification reactor can fully contact with the gas and speed up the reaction rate. The gas ejected from the oblique nozzles is obliquely ejected in the same direction, so that the bubbles move in the esterification reactor 2 in a rotating shape, so that the reacting materials can fully contact with the gas, and the reaction speed is accelerated.
优选地，所述加热管24为多个，呈平行均布在所述酯化反应器2内部；所述气体分布器25有多个，所述多个气体分布器25相互连通，所述每个气体分布器25的圆环管设在所述加热管24之间。Preferably, there are multiple heating pipes 24, which are parallel and evenly distributed inside the esterification reactor 2; there are multiple gas distributors 25, and the multiple gas distributors 25 communicate with each other. The circular pipes of two gas distributors 25 are arranged between the heating pipes 24.
利用上述的装置作为反应装置，一种催化酯化-分离耦合制备松香酯方法：Utilize above-mentioned device as reaction device, a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比1:1加入熔解釜1，再加入的甘油与松香重量的50％的松节油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为7.2Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质不断地流出，流出量≤12000m3/h，压力≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、松节油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、松节油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、松节油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量≤10000m3/h，压力≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为7.2MPa，反应0.5h后，酯化反应器2加热升温至275℃，控制反应温度保持在270℃～275℃范围内，反应压力为7.2MPa，在此反应条件下反应5.0h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为4.9mgKOH/g。Put glycerin (glycerol) and rosin into the melting pot 1 at a molar ratio of 1:1, then add glycerin and turpentine oil of 50% of the weight of rosin, heat and melt to form a mixed material, and passCO2 to press the material into the ester 2 in the esterification reactor, then the temperature was raised to 150°C, andCO2 was continuously introduced until the pressure in the esterification reactor 2 was 7.2Mpa, and then the gas outlet valve of the esterification reactor 2 was opened to make the water generated during the esterification reaction Steam, glycerin steam, turpentine steam, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, and the pressure is ≤10.0MPa. After being throttled and expanded by the expander 3, it enters the gas-liquid separator 4 and expands through the expander 3. Pressure reduction or throttling expansion pressure reduction ≤ 0.5MPa, temperature reduction ≤ 50 ℃, the gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, turpentine oil vapor, CO2 mixed gas phase substances, but water vapor, glycerin vapor, turpentine oil After the steam these outflowing materials enter the gas-liquid separator 4 through the expansion and depressurization of the expander 3, the water vapor, glycerin vapor, and turpentine vapor are condensed into liquid and separated from the gas-liquid separator 4, and enter the separation tower 6, and the separation tower 6 will The obtained water flows out from the bottom of the tower, and the remaining glycerin and turpentine are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, Gas flow ≤ 10000m3 /h, pressure ≤ 10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 7.2MPa. After reacting for 0.5h, the esterification reactor 2 is heated to 275°C, and the reaction temperature is controlled to remain within the range of 270°C to 275°C. The reaction pressure is 7.2MPa. Under the conditions of reaction for 5.0h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 4.9 mgKOH/g.
实施例2Example 2
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将乙醇和松香按摩尔比3:1加入熔解釜1，再加入的甘油与松香重量的25％的碳酸二甲酯，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为0.01Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤～50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、碳酸二甲酯打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为7.2MPa，反应0.5h后，酯化反应器2加热升温至290℃，控制反应温度保持在280℃～300℃范围内，反应压力为0.01MPa，在此反应条件下反应7.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为3.9mgKOH/g。Add ethanol and rosin in a molar ratio of 3:1 to the melting pot 1, then add glycerin and dimethyl carbonate of 25% of the weight of rosin, heat and melt to form a mixed material, and feedCO2 to press the material into the esterification reaction 2 in the reactor, then the temperature was raised to 150°C, and CO was continuously introduced until the pressure in the esterification reactor2 was 0.01Mpa, and then the gas outlet valve of the esterification reactor 2 was opened to make the water vapor generated during the esterification reaction, Glycerin vapor, dimethyl carbonate vapor, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, and the pressure is ≤10.0MPa. The expansion and depressurization or throttling expansion and decompression of machine 3 is ≤0.5MPa, and the temperature drop is ≤～50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, dimethyl carbonate vapor, and CO2 mixed gas phase substances, But water vapor, glycerin vapor, dimethyl carbonate vapor these outflowing materials enter gas-liquid separator 4 after expander 3 expands depressurization, water vapor, glycerin vapor, dimethyl carbonate vapor condense into liquid state from gas-liquid separator 4 is separated, enters in the separation tower 6, and the water of separation tower 6 flows out from the bottom of the tower, and the remaining glycerol and dimethyl carbonate are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 7.2MPa. After reacting for 0.5h, the esterification reactor 2 is heated to 290°C, and the reaction temperature is controlled to remain within the range of 280°C to 300°C. The reaction pressure is 0.01MPa. Under the conditions of reaction for 7.5 hours, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 3.9 mgKOH/g.
实施例3Example 3
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比5:1加入熔解釜1，再加入的甘油与松香重量的10％的200#溶剂油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至100℃，并不断通入CO2至酯化反应器2内压力为3.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、200#溶剂油蒸汽、CO2混合气相物质不断地流出，流出 量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、200#溶剂油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、200#溶剂油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、200#溶剂油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、200#溶剂油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为3.0MPa，反应1.0h后，酯化反应器2加热升温至280℃，控制反应温度保持在270℃～290℃范围内，反应压力为3.0MPa，在此反应条件下反应3.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为2.4mgKOH/g。Glycerin (glycerol) and rosin are added into the melting tank 1 at a molar ratio of 5:1, and the added glycerin and rosin weight of 10% 200# solvent oil are heated and melted to form a mixed material, andCO is introduced to dissolve the material Press into the esterification reactor 2, then raise the temperature to 100°C, and continuously feedCO2 until the pressure in the esterification reactor 2 is 3.0Mpa, and then open the gas outlet valve of the esterification reactor 2, so that during the esterification reaction The generated water vapor, glycerin vapor, 200# solvent oil vapor, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, the pressure is ≤10.0MPa, and enters the gas-liquid separation after being throttled and expanded by the expander 3 The device 4 is expanded and depressurized by the expander 3 or throttling expansion and depressurized to ≤0.5MPa, and the temperature is lowered to ≤50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, 200# solvent oil vapor, CO2 Mixed gas phase substances, but water vapor, glycerin steam, 200# solvent oil steam, these outflowing materials are expanded and decompressed by expander 3 and enter gas-liquid separator 4, water vapor, glycerin steam, 200# solvent oil steam are condensed into liquid state from The gas-liquid separator 4 is separated and enters the separation tower 6, and the separation tower 6 flows out the water obtained from the bottom of the tower, and the remaining glycerin and 200# solvent oil are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 3.0MPa. After the reaction for 1.0h, the esterification reactor 2 is heated to 280°C, and the reaction temperature is controlled to remain in the range of 270°C to 290°C. The reaction pressure is 3.0MPa. Under the conditions of reaction for 3.5 hours, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 2.4 mgKOH/g.
实施例4Example 4
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比10:1加入熔解釜1，再加入的甘油与松香重量的20％的矿物精油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至200℃，并不断通入CO2至酯化反应器2内压力为10.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、矿物精油蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、矿物精油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、矿物精油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、矿物精油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、矿物精油打回系统循环使用。而从气液分离器4中分离出来的CO2 进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为10.0MPa，反应0.5h后，酯化反应器2加热升温至200℃，控制反应温度保持在190℃～210℃范围内，反应压力为10.0MPa，在此反应条件下反应7.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为2.4mgKOH/g。Add glycerol (glycerol) and rosin into melting tank 1 at a molar ratio of 10:1, then add glycerin and 20% mineral essential oil of rosin weight, heat and melt to form a mixed material, and feedCO2 to press the material into 2 in the esterification reactor, then raise the temperature to 200°C, and continuously feedCO2 until the pressure in the esterification reactor 2 is 10.0Mpa, and then open the valve of the gas outlet of the esterification reactor 2 to make the gas generated during the esterification reaction Water vapor, glycerin vapor, mineral essential oil vapor, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, and the pressure is ≤10.0MPa. After throttling and expanding by the expander 3, it enters the gas-liquid separator 4 and passes through The expansion and pressure reduction of the expander 3 or throttling expansion and pressure reduction is ≤0.5MPa, and the temperature drop is ≤50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, mineral essential oil vapor, and CO2 mixed gas phase substances, but water After steam, glycerin steam, and mineral essential oil steam flow out of the gas-liquid separator 4 after being expanded and depressurized by the expander 3, the water vapor, glycerin steam, and mineral essential oil steam are condensed into liquid and separated from the gas-liquid separator 4, and then enter the gas-liquid separator 4. In the tower 6, the separation tower 6 flows out the obtained water from the bottom of the tower, and the remaining glycerin and mineral essential oil are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 10.0MPa. After the reaction for 0.5h, the esterification reactor 2 is heated to 200°C, and the reaction temperature is controlled to remain within the range of 190°C to 210°C. The reaction pressure is 10.0MPa. Under the conditions of reaction for 7.5 hours, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 2.4 mgKOH/g.
实施例5Example 5
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比6:1加入熔解釜1，再加入的甘油与松香重量的15％的松节油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为6.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、松节油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、松节油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、松节油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为6.0MPa，反应0.5h后，酯化反应器2加热升温至180℃，控制反应温度保持在170℃～190℃范围内，反应压力为6.0MPa，在此反应条件下反应0.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为9.1mgKOH/g。Put glycerin (glycerol) and rosin into melting kettle 1 at a molar ratio of 6:1, then add glycerin and 15% turpentine by weight of rosin, heat and melt to form a mixed material, and feedCO2 to press the material into the ester 2 in the esterification reactor, then the temperature was raised to 150°C, andCO2 was continuously introduced until the pressure in the esterification reactor 2 was 6.0Mpa, and then the gas outlet valve of the esterification reactor 2 was opened to make the water generated during the esterification reaction Steam, glycerin steam, turpentine steam, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, and the pressure is ≤10.0MPa. After being throttled and expanded by the expander 3, it enters the gas-liquid separator 4 and passes through the expander. 3 Expansion and decompression or throttling expansion and decompression to ≤0.5MPa, temperature drop ≤50°C, the gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, turpentine vapor, CO2 mixed gas phase substances, but water vapor, glycerin After steam and turpentine steam are expanded and decompressed by the expander 3 and enter the gas-liquid separator 4, water vapor, glycerin steam, and turpentine steam are condensed into liquid and separated from the gas-liquid separator 4, and enter the separation tower 6 for separation. Tower 6 flows out the obtained water from the bottom of the tower, and the remaining glycerin and turpentine are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 6.0MPa. After 0.5h of reaction, the esterification reactor 2 is heated up to 180°C, and the reaction temperature is controlled to remain in the range of 170°C to 190°C. The reaction pressure is 6.0MPa. Under the conditions of reaction for 0.5h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 9.1 mgKOH/g.
实施例6Example 6
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction unit that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比4:1加入熔解釜1，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为5.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为5.0MPa，反应0.5h后，酯化反应器2加热升温至160℃，控制反应温度保持在150℃～170℃范围内，反应压力为5.0.0MPa，在此反应条件下反应2.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为3.2mgKOH/g。Glycerol (glycerol) and rosin are added into the melting tank 1 in a molar ratio of 4:1, heated and melted to form a mixed material, and CO is introduced to press the material into the esterification reactor2 , and then the temperature is raised to 150 ° C, and Continuously feedCO2 until the pressure in the esterification reactor 2 is 5.0Mpa, and then open the gas outlet valve of the esterification reactor 2, so that the water vapor, glycerin vapor, andCO2 mixed gas phase substances generated during the esterification reaction flow out continuously , the outflow is ≤12000m3 /h, the pressure is ≤10.0MPa, it enters the gas-liquid separator 4 after being throttled and expanded by the expander 3, and the expansion and pressure reduction by the expander 3 or throttling expansion and pressure reduction is ≤0.5MPa, and the temperature is lowered ≤50°C, the gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, and CO2 mixed gas phase substances, but the water vapor, glycerin vapor and other substances flowing out are expanded and depressurized by the expander 3 and enter the gas-liquid separator 4 , water vapor and glycerin vapor are condensed into a liquid state and separated from the gas-liquid separator 4, and enter the separation tower 6, and the separation tower 6 flows out the water obtained from the bottom of the tower, and the remaining glycerin is returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 5.0MPa. After reacting for 0.5h, the esterification reactor 2 is heated up to 160°C, and the reaction temperature is controlled to remain within the range of 150°C to 170°C. The reaction pressure is 5.0.0MPa. React for 2.5 hours under the reaction conditions to obtain the product, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 3.2 mgKOH/g.
实施例7Example 7
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比1:1加入熔解釜1，再加入的甘油与松香重量的45％的松节油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为7.2Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质不断地流出，流出量为≤12000 m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、松节油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、松节油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、松节油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为7.2MPa，反应0.5h后，酯化反应器2加热升温至275℃，控制反应温度保持在270℃～280℃范围内，反应压力为7.2MPa，在此反应条件下反应2.0h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为8.4mgKOH/g。Put glycerin (glycerol) and rosin into the melting pot 1 at a molar ratio of 1:1, then add glycerin and turpentine with a weight of 45% of rosin, heat and melt to form a mixed material, and passCO2 to press the material into the ester 2 in the esterification reactor, then the temperature was raised to 150°C, andCO2 was continuously introduced until the pressure in the esterification reactor 2 was 7.2Mpa, and then the gas outlet valve of the esterification reactor 2 was opened to make the water generated during the esterification reaction Steam, glycerin steam, turpentine steam, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000 m3 /h, and the pressure is ≤10.0MPa. After being throttled and expanded by the expander 3, it enters the gas-liquid separator 4, and after expansion Machine 3 expansion and pressure reduction or throttling expansion and pressure reduction is ≤0.5MPa, and the temperature drop is ≤50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, turpentine oil vapor, and CO2 Mixed gas phase substances, but water vapor, Glycerin steam, turpentine steam, these outflowing substances are expanded and depressurized by the expander 3 and then enter the gas-liquid separator 4. After the water vapor, glycerin steam, and turpentine steam are condensed into liquids, they are separated from the gas-liquid separator 4 and enter the separation tower 6. The separation tower 6 flows out the water obtained from the bottom of the tower, and the remaining glycerin and turpentine are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 7.2MPa. After reacting for 0.5h, the esterification reactor 2 is heated to 275°C, and the reaction temperature is controlled to remain within the range of 270°C to 280°C. The reaction pressure is 7.2MPa. Under the condition of reaction for 2.0h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 8.4 mgKOH/g.
实施例8Example 8
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比1:1加入熔解釜1，再加入的甘油与松香重量的3％的碳酸二甲酯，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为8.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、碳酸二甲酯打回系统循环使用。而从气液分离器4中分 离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为8.0MPa，反应0.5h后，酯化反应器2加热升温至200℃，控制反应温度保持在190℃～210℃范围内，反应压力为8.0MPa，在此反应条件下反应1.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为11.2mgKOH/g。Glycerol (glycerol) and rosin are added into the melting tank 1 at a molar ratio of 1:1, and then added glycerin and dimethyl carbonate of 3% of the weight of the rosin are heated and melted to form a mixed material, andCO is introduced to dissolve the material Press into the esterification reactor 2, then raise the temperature to 150°C, and continuously feedCO2 until the pressure in the esterification reactor 2 is 8.0Mpa, then open the valve of the gas outlet of the esterification reactor 2, so that during the esterification reaction The generated water vapor, glycerin vapor, dimethyl carbonate vapor, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, the pressure is ≤10.0MPa, and enters the gas-liquid separation after being throttled and expanded by the expander 3 The device 4 is expanded and depressurized by the expander 3 or throttling expansion and depressurized to ≤0.5MPa, and the temperature is lowered to ≤50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, dimethyl carbonate vapor, CO2 Mixed gas phase substances, but after the outflowing materials such as water vapor, glycerin vapor, and dimethyl carbonate vapor are expanded and decompressed by the expander 3 and enter the gas-liquid separator 4, the water vapor, glycerin vapor, and dimethyl carbonate vapor are condensed into liquid state from The gas-liquid separator 4 is separated and enters the separation tower 6, and the separation tower 6 flows out the water obtained from the bottom of the tower, and the remaining glycerin and dimethyl carbonate are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 8.0MPa. After reacting for 0.5h, the esterification reactor 2 is heated up to 200°C, and the reaction temperature is controlled to remain in the range of 190°C to 210°C. The reaction pressure is 8.0MPa. Under the conditions of reaction for 1.5h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 11.2 mgKOH/g.
实施例9Example 9
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甲醇和松香按摩尔比2:1加入熔解釜1，再加入的甘油与松香重量的35％的松节油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至200℃，并不断通入CO2至酯化反应器2内压力为1.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、松节油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、松节油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、松节油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为1.0MPa，反应0.5h后，酯化反应器2加热升温至250℃，控制反应温度保持在245℃～255℃范围内，反应压力为1.0MPa，在此反应条件下反应4.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为3.1mgKOH/g。Add methanol and rosin in a molar ratio of 2:1 to melting kettle 1, then add glycerin and 35% turpentine of rosin weight, heat and melt to form a mixed material, feed CO2 and press the material into the esterification reactor 2 , then the temperature was raised to 200°C, and CO was continuously introduced until the pressure in the esterification reactor2 was 1.0Mpa, and then the gas outlet valve of the esterification reactor 2 was opened to make the water vapor, glycerin vapor, and The turpentine vapor and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, and the pressure is ≤10.0MPa. After throttling and expanding by the expander 3, it enters the gas-liquid separator 4, and expands and depressurizes through the expander 3 or Throttling expansion and pressure reduction is ≤0.5MPa, temperature drop ≤50°C, the gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, turpentine vapor, CO2 mixed gas phase substances, but water vapor, glycerin vapor, turpentine vapor, etc. After the material flowing out enters the gas-liquid separator 4 through expansion and depressurization of the expander 3, water vapor, glycerin vapor, and turpentine vapor are condensed into liquids and separated from the gas-liquid separator 4, and enter the separation tower 6, and the separation tower 6 converts the obtained Water flows out from the bottom of the tower, and the remaining glycerin and turpentine are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 1.0MPa. After the reaction for 0.5h, the esterification reactor 2 is heated to 250°C, and the reaction temperature is controlled to remain within the range of 245°C to 255°C. The reaction pressure is 1.0MPa. Under the condition of reaction for 4.5h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 3.1 mgKOH/g.
实施例10Example 10
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比9:1加入熔解釜1，再加入的甘油与松香重量的24％的碳酸二甲酯，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至150℃，并不断通入CO2至酯化反应器2内压力为4.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、碳酸二甲酯打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为4.0MPa，反应1.5h后，酯化反应器2加热升温至270℃，控制反应温度保持在265℃～275℃范围内，反应压力为4.0MPa，在此反应条件下反应2.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为1.7mgKOH/g。Glycerol (glycerol) and rosin are added into the melting tank 1 in a molar ratio of 9:1, and the added glycerol and dimethyl carbonate of 24% of the weight of rosin are heated and melted to form a mixed material, andCO is fed into the material Press into the esterification reactor 2, then raise the temperature to 150°C, and continuously feedCO2 until the pressure in the esterification reactor 2 is 4.0Mpa, and then open the valve of the gas outlet of the esterification reactor 2, so that during the esterification reaction The generated water vapor, glycerin vapor, dimethyl carbonate vapor, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, the pressure is ≤10.0MPa, and enters the gas-liquid separation after being throttled and expanded by the expander 3 The device 4 is expanded and depressurized by the expander 3 or throttling expansion and depressurized to ≤0.5MPa, and the temperature is lowered to ≤50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, dimethyl carbonate vapor, CO2 Mixed gas phase substances, but after the outflowing materials such as water vapor, glycerin vapor, and dimethyl carbonate vapor are expanded and decompressed by the expander 3 and enter the gas-liquid separator 4, the water vapor, glycerin vapor, and dimethyl carbonate vapor are condensed into liquid state from The gas-liquid separator 4 is separated and enters the separation tower 6, and the separation tower 6 flows out the water obtained from the bottom of the tower, and the remaining glycerin and dimethyl carbonate are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 4.0MPa. After 1.5 hours of reaction, the esterification reactor 2 was heated to 270°C, and the reaction temperature was controlled to remain within the range of 265°C to 275°C. The reaction pressure was 4.0MPa. Under the condition of reaction for 2.5h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 1.7 mgKOH/g.
实施例11Example 11
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比1:1加入熔解釜1，再加入的甘油与松香重量的5％的松节油，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至160℃，并不断通入CO2至酯化反应器2内压力为 8.0Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、松节油蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、松节油蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、松节油蒸汽冷凝为液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、松节油打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为8.0MPa，反应0.5h后，酯化反应器2加热升温至200℃，控制反应温度保持在190℃～210℃范围内，反应压力为8.0MPa，在此反应条件下反应5.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为4.4mgKOH/g。Add glycerin (glycerol) and rosin to melting kettle 1 at a molar ratio of 1:1, then add glycerin and 5% turpentine by weight of rosin, heat and melt to form a mixed material, and feedCO2 to press the material into the ester 2 in the esterification reactor, then the temperature was raised to 160°C, andCO2 was continuously introduced until the pressure in the esterification reactor 2 was 8.0Mpa, and then the gas outlet valve of the esterification reactor 2 was opened to make the water generated during the esterification reaction Steam, glycerin steam, turpentine steam, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, and the pressure is ≤10.0MPa. After being throttled and expanded by the expander 3, it enters the gas-liquid separator 4 and passes through the expander. 3 Expansion and decompression or throttling expansion and decompression to ≤0.5MPa, temperature drop ≤50°C, the gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, turpentine vapor, CO2 mixed gas phase substances, but water vapor, glycerin After steam and turpentine steam are expanded and decompressed by the expander 3 and enter the gas-liquid separator 4, water vapor, glycerin steam, and turpentine steam are condensed into liquid and separated from the gas-liquid separator 4, and enter the separation tower 6 for separation. Tower 6 flows out the obtained water from the bottom of the tower, and the remaining glycerin and turpentine are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 8.0MPa. After reacting for 0.5h, the esterification reactor 2 is heated up to 200°C, and the reaction temperature is controlled to remain in the range of 190°C to 210°C. The reaction pressure is 8.0MPa. Under the condition of reaction for 5.5h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 4.4 mgKOH/g.
实施例12Example 12
使用的反应装置与实施例1相同，一种催化酯化-分离耦合制备松香酯方法：The reaction device that uses is identical with embodiment 1, and a kind of catalytic esterification-separation coupling prepares rosin ester method:
将甘油(丙三醇)和松香按摩尔比3:1加入熔解釜1，再加入的甘油与松香重量的20％的碳酸二甲酯，加热，熔解，形成混合物料，通入CO2将物料压进酯化反应器内2，随后升温至200℃，并不断通入CO2至酯化反应器2内压力为5.6Mpa，然后打开酯化反应器2出气口阀门，使酯化反应过程中产生的水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质不断地流出，流出量为≤12000m3/h，压力为≤10.0MPa，经膨胀机3节流膨胀后进入气液分离器4，经膨胀机3膨胀降压或节流膨胀降压为≤0.5MPa，降温≤50℃，从酯化反应器2流出的气相含有水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽、CO2混合气相物质，但是水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽这些流出的物质经膨胀机3膨胀降压进入气液分离器4后，水蒸汽、甘油蒸汽、碳酸二甲酯蒸汽冷凝为 液态从气液分离器4分离出来，进入分离塔6中，分离塔6将所得的水从塔底流出，余下的甘油、碳酸二甲酯打回系统循环使用。而从气液分离器4中分离出来的CO2进入透平压缩机5中加压循环回酯化反应器2进行酯化反应，经透平压缩机5加压流回酯化反应器2，气体流量为≤10000m3/h，压力为≤10.0MPa。透平机压缩机5进行做功是上述膨胀机3膨胀做功推动透平压缩机6加压。并维持酯化反应器的压力为5.6MPa，反应0.5h后，酯化反应器2加热升温至295℃，控制反应温度保持在290℃～300℃范围内，反应压力为5.6MPa，在此反应条件下反应1.5h，即得产品，所得松香酯从酯化反应器2的出料口流出。经检测，所得松香酯酸值为4.1mgKOH/g。Glycerol (glycerol) and rosin are added into the melting tank 1 in a molar ratio of 3:1, and the added glycerin and dimethyl carbonate of 20% of the weight of the rosin are heated and melted to form a mixed material, andCO is introduced to dissolve the material Press into the esterification reactor 2, then raise the temperature to 200°C, and continuously feedCO2 until the pressure in the esterification reactor 2 is 5.6Mpa, then open the valve of the gas outlet of the esterification reactor 2, so that during the esterification reaction The generated water vapor, glycerin vapor, dimethyl carbonate vapor, and CO2 mixed gas phase substances continuously flow out, the outflow volume is ≤12000m3 /h, the pressure is ≤10.0MPa, and enters the gas-liquid separation after being throttled and expanded by the expander 3 The device 4 is expanded and depressurized by the expander 3 or throttling expansion and depressurized to ≤0.5MPa, and the temperature is lowered to ≤50°C. The gas phase flowing out from the esterification reactor 2 contains water vapor, glycerin vapor, dimethyl carbonate vapor, CO2 Mixed gas phase substances, but after the outflowing materials such as water vapor, glycerin vapor, and dimethyl carbonate vapor are expanded and decompressed by the expander 3 and enter the gas-liquid separator 4, the water vapor, glycerin vapor, and dimethyl carbonate vapor are condensed into liquid state from The gas-liquid separator 4 is separated and enters the separation tower 6, and the separation tower 6 flows out the water obtained from the bottom of the tower, and the remaining glycerin and dimethyl carbonate are returned to the system for recycling. And the CO separated from the gas-liquid separator4 enters the turbo compressor 5 and pressurizes and circulates back to the esterification reactor 2 to carry out the esterification reaction, and flows back to the esterification reactor 2 through the turbo compressor 5 pressurized, The gas flow rate is ≤10000m3 /h, and the pressure is ≤10.0MPa. The work performed by the turbine compressor 5 is that the above-mentioned expander 3 expands and works to push the turbo compressor 6 to pressurize. And maintain the pressure of the esterification reactor at 5.6MPa. After 0.5h of reaction, the esterification reactor 2 is heated up to 295°C, and the reaction temperature is controlled to remain in the range of 290°C to 300°C. The reaction pressure is 5.6MPa. Under the conditions of reaction for 1.5h, the product is obtained, and the obtained rosin ester flows out from the outlet of the esterification reactor 2. After testing, the acid value of the obtained rosin ester was 4.1 mgKOH/g.
本发明具体实施例中，如果装置处于不反应状态，既不添加反应气时，反应系统内流量皆为0，采出气相温度等也为0。In a specific embodiment of the present invention, if the device is in a non-reactive state, when no reaction gas is added, the flow rate in the reaction system is 0, and the temperature of the gas phase produced is also 0.
| Application Number | Priority Date | Filing Date | Title |
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| CN201510082024.0ACN104694014B (en) | 2015-02-15 | 2015-02-15 | Trans-critical cycle CO2Catalytic esterification separation coupling prepares the method and device of rosin ester |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510082024.0ACN104694014B (en) | 2015-02-15 | 2015-02-15 | Trans-critical cycle CO2Catalytic esterification separation coupling prepares the method and device of rosin ester |
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| CN201510082024.0AActiveCN104694014B (en) | 2015-02-15 | 2015-02-15 | Trans-critical cycle CO2Catalytic esterification separation coupling prepares the method and device of rosin ester |
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| CN110143990A (en)* | 2019-05-31 | 2019-08-20 | 广西大学 | A method for preparing food-grade rosin xylose ester by catalytic esterification-separation coupling |
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