CN107935846B - Device and method for continuously producing environment-friendly plasticizer - Google Patents
Device and method for continuously producing environment-friendly plasticizer Download PDFInfo
- Publication number
- CN107935846B CN107935846B CN201711070334.6A CN201711070334A CN107935846B CN 107935846 B CN107935846 B CN 107935846B CN 201711070334 A CN201711070334 A CN 201711070334A CN 107935846 B CN107935846 B CN 107935846B
- Authority
- CN
- China
- Prior art keywords
- kettle
- reaction
- esterification reaction
- dehydration
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004014 plasticizer Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 79
- 208000005156 Dehydration Diseases 0.000 claims abstract description 41
- 230000018044 dehydration Effects 0.000 claims abstract description 41
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000010924 continuous production Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000011973 solid acid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000032050 esterification Effects 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 8
- 238000009434 installation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- KFROBPVFLIZCHZ-UHFFFAOYSA-N bis(6-methylheptyl) benzene-1,4-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C=C1 KFROBPVFLIZCHZ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
-
- 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
- B01J19/1862—Stationary reactors having moving elements inside placed in series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种连续化生产环保型增塑剂的装置和方法，将固体酸和液体醇物料加入到预热脱水釜中，搅拌升温至无水脱出，实现物料预热和脱水处理；将上述预热脱水后的反应物料由预热脱水釜通过泵或高位压差输送到串联的多级酯化反应釜中，向首级酯化反应釜中添加催化剂，搅拌升温进行反应；随着反应物料的连续输入，酯化反应釜中的反应物料达到釜上部出料口时，输送到下一级酯化反应釜内继续反应，调控物料进入酯化反应釜进中的流量，反应结束的物液输送到到脱醇釜内进行连续脱醇处理。本发明装置布局合理，工序简单，生产效率高，运行稳定，有效提高单位时间内的产量，实现环保增塑剂的连续化和规模化批量生产。
A device and method for continuous production of environmentally friendly plasticizers. The solid acid and liquid alcohol materials are added into a preheated dehydration kettle, and the temperature is stirred and heated to anhydrous dehydration, so as to realize the material preheating and dehydration treatment; The latter reaction material is transported from the preheating dehydration kettle to the multi-stage esterification reaction kettle in series through a pump or a high pressure difference, a catalyst is added to the first-stage esterification reaction kettle, and the temperature is stirred and heated to carry out the reaction; with the continuous input of the reaction material , when the reaction material in the esterification reaction kettle reaches the discharge port on the upper part of the kettle, it is transported to the next-stage esterification reaction kettle to continue the reaction, and the flow rate of the material entering the esterification reaction kettle is regulated and controlled, and the material and liquid after the reaction is transported to the Continuous dealcoholization treatment is carried out in the dealcoholization tank. The device of the invention has reasonable layout, simple procedure, high production efficiency and stable operation, effectively improves the output per unit time, and realizes the continuous and large-scale mass production of the environment-friendly plasticizer.
Description
技术领域technical field
本发明属于环保塑料助剂制备技术领域，特别是涉及一种连续化生产环保型增塑剂的方法。The invention belongs to the technical field of preparation of environment-friendly plastic additives, in particular to a method for continuous production of environment-friendly plasticizers.
背景技术Background technique
电缆被誉为国民经济的“血管”和“神经”。电线电缆制造业是国民经济中最大的配套行业之一，是机械行业中仅次于汽车行业的第二大产业，电线电缆产品广泛应用于能源、交通、通信、汽车以及石油化工等产业，近年来，我国电线电缆行业保持了较快发展势头，继续在国民经济中占据重要地位。随着本国工业化发展程度的提高，基础建设的完善，城市化水平的提高，线缆行业必将走向成熟和快速化发展。Cables are known as the "blood vessels" and "nerves" of the national economy. The wire and cable manufacturing industry is one of the largest supporting industries in the national economy and the second largest industry in the machinery industry after the automobile industry. Wire and cable products are widely used in energy, transportation, communications, automobiles and petrochemical industries. Since then, my country's wire and cable industry has maintained a rapid development momentum and continues to occupy an important position in the national economy. With the improvement of the country's industrialization development, the improvement of infrastructure, and the improvement of the level of urbanization, the cable industry is bound to mature and develop rapidly.
环保增塑剂对苯二甲酸二异辛酯(DOTP)是一种用途广泛、性能优良的精细化工产品，其主要应用于PVC塑料制品中，是生产电缆料的主要添加剂。伴随着电缆行业的快速发展，其需求量将日益增加，具有广泛的市场前景。Diisooctyl terephthalate (DOTP), an environmentally friendly plasticizer, is a fine chemical product with a wide range of uses and excellent performance. It is mainly used in PVC plastic products and is the main additive for the production of cable materials. With the rapid development of the cable industry, its demand will increase day by day, and it has a broad market prospect.
目前工业化生产DOTP的主要采用间歇法，主要存在以下缺点：1)间歇式生产耗时较长，产品质量波动大，不太稳定；2)工艺落后，劳动强度大；3)间歇酯化能耗、物耗高，产品收率低；4)规模小，无法实现规模化生产，制约了增塑剂的产量。因反应采用大量回收的PTA料为原料，粒径不均匀，造成固液酯化反应相容性差，反应耗时长等缺陷。本发明提出一种工艺稳定，经济效应高的新方法，实现环保增塑剂的连续化和规模化生产。At present, the industrial production of DOTP mainly adopts the batch method, which mainly has the following disadvantages: 1) The batch production takes a long time, and the product quality fluctuates greatly, which is not stable; 2) The process is backward and labor-intensive; 3) The intermittent esterification consumes energy , high material consumption, low product yield; 4) small scale, can not achieve large-scale production, restricting the output of plasticizers. Because the reaction uses a large amount of recovered PTA material as the raw material, the particle size is not uniform, resulting in poor compatibility of the solid-liquid esterification reaction and long reaction time. The invention proposes a new method with stable process and high economic effect, and realizes the continuous and large-scale production of the environment-friendly plasticizer.
发明内容SUMMARY OF THE INVENTION
解决的技术问题：本发明的目的在于提供一种连续化生产环保型增塑剂的装置及方法。Technical problem to be solved: The purpose of the present invention is to provide a device and method for continuous production of environmentally friendly plasticizers.
技术方案：一种连续化生产环保型增塑剂的方法，包括以下步骤：(1)物料预热脱水：将固体酸和液体醇物料按质量比例1:2.4-1:3.2加入到预热脱水釜中，搅拌升温，釜内温度大于160℃至无水脱出，实现物料预热和脱水处理；(2)连续酯化反应：将上述预热脱水后的反应物料由预热脱水釜通过泵或高位压差输送到串联的多级酯化反应釜中，向首级酯化反应釜中添加催化剂，所述催化剂为钛酸四丁酯，添加量为反应总物料的0.1wt.％-0.5wt.％，搅拌升温至180-240℃进行反应；随着反应物料的连续输入，酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵输送到下一级酯化反应釜内继续反应，控制各个串联酯化反应釜中反应温度180-240℃，调控物料进入酯化反应釜进中的流量，使得最后一个酯化反应釜中流出物液酸值小于0.50mgKOH/g，反应结束的物液输送到到脱醇釜内进行连续脱醇处理。Technical scheme: a method for continuous production of environmentally friendly plasticizers, comprising the following steps: (1) material preheating dehydration: adding solid acid and liquid alcohol material to the preheating dehydration in a mass ratio of 1:2.4-1:3.2 In the kettle, the temperature is increased by stirring, and the temperature in the kettle is greater than 160 ° C to anhydrous dehydration, so as to realize material preheating and dehydration treatment; (2) Continuous esterification reaction: the above-mentioned preheated and dehydrated reaction materials are passed from the preheated dehydration kettle through a pump or The high-level pressure difference is transported to the multi-stage esterification reaction kettle in series, and a catalyst is added to the first-stage esterification reaction kettle. The catalyst is tetrabutyl titanate, and the addition amount is 0.1wt.%-0.5wt of the total reaction material. .%, stir and heat up to 180-240 ℃ to carry out the reaction; with the continuous input of the reaction material, when the reaction material in the esterification reaction kettle reaches the discharge port at the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the next step through the pump. Continue the reaction in the grade esterification reaction kettle, control the reaction temperature in each serial esterification reaction kettle to 180-240 °C, and control the flow rate of the material entering the esterification reaction kettle, so that the acid value of the effluent in the last esterification reaction kettle is less than 0.50mgKOH/g, the liquid after the reaction is transported to the dealcoholization kettle for continuous dealcoholization treatment.
上述步骤(1)中固体酸原料为精对苯二甲酸、PTA水池料、PTA落地料或聚酯纤维行业中碱减量工艺中的回收料(俗称PTA碱溶料)。In the above-mentioned step (1), the solid acid raw material is purified terephthalic acid, PTA pool material, PTA floor material or recycled material (commonly referred to as PTA alkali solvent material) in the alkali reduction process in the polyester fiber industry.
上述步骤(2)中串联的多级酯化反应釜的数量至少为两级。In the above-mentioned step (2), the number of the multi-stage esterification reactors connected in series is at least two levels.
上述步骤(2)中酯化反应在串联的多级流化床反应器中进行，串联的流化床反应器的数量至少为两级。In the above-mentioned step (2), the esterification reaction is carried out in multi-stage fluidized bed reactors connected in series, and the number of fluidized bed reactors connected in series is at least two stages.
上述步骤(2)中催化剂钛酸四丁酯添加量为反应总物料的0.1wt.％-0.3wt.％。In the above step (2), the addition amount of the catalyst tetrabutyl titanate is 0.1wt.%-0.3wt.% of the total reaction material.
一种连续化生产环保型增塑剂的装置，该装置通过管道依次连接有预热脱水釜、串联的多级酯化反应装置和脱醇釜；所述预热脱水釜设有冷凝器和废水接收罐；所述串联的多级酯化反装置由至少两级串联的酯化反应釜或者串联的流化床反应器组成，第一级酯化反应装置通过计量泵与催化剂储罐连接，最后一个酯化反应装置通过管道与脱醇釜连接。A device for continuous production of environmentally friendly plasticizers, the device is sequentially connected with a preheating dehydration kettle, a series-connected multi-stage esterification reaction device and a dealcoholization kettle; the preheating dehydration kettle is provided with a condenser and waste water Receiving tank; the multi-stage esterification reaction device in series is composed of at least two-stage series-connected esterification reaction kettles or series-connected fluidized bed reactors, the first-stage esterification reaction device is connected with the catalyst storage tank through a metering pump, and finally An esterification reaction device is connected with the dealcoholization kettle through pipelines.
上述多级酯化反应装置中的各级装置的安装高度依次降低，反应物料通过自然溢流到相邻下一级酯化反应釜中。The installation heights of the devices of each level in the above-mentioned multi-stage esterification reaction device are successively reduced, and the reaction material is naturally overflowed into the adjacent next-level esterification reaction kettle.
上述多级酯化反应装置中的各级装置的安装高度相同，反应物料通过泵输送到相邻下一级酯化反应装置中。In the above-mentioned multi-stage esterification reaction device, the installation heights of each stage of the device are the same, and the reaction material is transported to the adjacent next-stage esterification reaction device through a pump.
上述各级酯化反应釜的釜顶连接有冷凝器和醇水分离器，所述冷凝后的异辛醇由所述醇水分离器经管道流入对应酯化反应釜中。The tops of the above-mentioned esterification reaction kettles are connected with a condenser and an alcohol-water separator, and the condensed iso-octanol flows into the corresponding esterification reaction kettles through a pipeline through the alcohol-water separator.
上述串联的各级酯化反应装置接入一个冷凝器中统一冷凝和换热，并将冷凝后的异辛醇输送到各级酯化反应釜中。The above-mentioned series-connected esterification reaction units at all levels are connected to a condenser for unified condensation and heat exchange, and the condensed isooctanol is transported to the esterification reaction kettles of all levels.
有益效果：本发明提供一种连续化生产环保型增塑剂的装置及方法，本发明在反应前将固液反应物料通过脱水釜进行预热和脱水预处理，实现物料的整体均匀流动性，显著加快物料转移速度和反应速度。本发明采用串联的酯化反应釜或者流化床反应器，通过自然溢流和泵输送的方式实现反应连续化，且本发明装置布局合理，工序简单，生产效率高，运行稳定，有效提高单位时间内的产量，实现环保增塑剂的连续化和规模化批量生产。Beneficial effects: The present invention provides a device and method for continuous production of environmentally friendly plasticizers. The present invention preheats and dehydrates the solid-liquid reaction material through a dehydration kettle before the reaction, so as to realize the overall uniform fluidity of the material, Significantly speed up material transfer and reaction speed. The invention adopts esterification reaction kettles or fluidized bed reactors connected in series, and realizes the continuous reaction by means of natural overflow and pump conveying, and the device of the invention has reasonable layout, simple process, high production efficiency, stable operation, and effectively improves the unit The output within time can realize the continuous and large-scale mass production of environmentally friendly plasticizers.
附图说明Description of drawings
图1为本发明优选的四个酯化反应釜串联的连续化生产环保型增塑剂的装置图。Fig. 1 is the device diagram of the continuous production of environment-friendly plasticizer with four preferred esterification reactors connected in series in the present invention.
图2为本发明优选的六个酯化反应釜串联的连续化生产环保型增塑剂的装置图。Fig. 2 is the device diagram of the continuous production of environment-friendly plasticizers with the preferred six esterification reactors connected in series in the present invention.
图中，1：预热脱水釜，2：一号酯化反应釜，3：催化剂计量泵，4：二号酯化反应釜，5：三号酯化反应釜，6：四号酯化反应釜，7：五号酯化反应釜，8：六号酯化反应釜，9：脱醇釜。In the figure, 1: preheating dehydration kettle, 2: No. 1 esterification reaction kettle, 3: catalyst metering pump, 4: No. 2 esterification reaction kettle, 5: No. 3 esterification reaction kettle, 6: No. 4 esterification reaction kettle Kettle, 7: No. 5 esterification reactor, 8: No. 6 esterification reactor, 9: Dealcoholization reactor.
图1为本发明优选的四个酯化反应釜串联的连续化生产环保型增塑剂的装置图，如图1所示，所述预热脱水后的反应物料由预热脱水釜通过泵输送入到酯化体系中的一号酯化反应釜中，且所述酯化体系中四个酯化反应釜安装高度依次降低，反应物料通过自然溢流方式流入到相邻下一个酯化反应釜中。Fig. 1 is the device diagram of the continuous production of environment-friendly plasticizers in the preferred series of four esterification reaction kettles of the present invention, as shown in Fig. 1, the reaction material after the preheating dehydration is transported by the preheating dehydration kettle by pump Into the No. 1 esterification reaction kettle in the esterification system, and the installation heights of the four esterification reaction kettles in the esterification system are reduced in turn, and the reaction material flows into the adjacent next esterification reaction kettle through natural overflow middle.
图2为本发明优选的六个酯化反应釜串联的连续化生产环保型增塑剂的装置图，如图2所示，所述预热脱水后的反应物料由预热脱水釜通过高位差输送入到酯化体系中的一号酯化反应釜中，且所述酯化体系中六个酯化反应釜安装高度相同，反应物料通过泵按一定流量送入到相邻下一个酯化反应釜中。Fig. 2 is the device diagram of the preferred continuous production of environmental-friendly plasticizers in series of six esterification reaction kettles of the present invention, as shown in Fig. 2, the reaction material after the preheating dehydration is passed through the high level difference by the preheating dehydration kettle It is transported into the No. 1 esterification reaction kettle in the esterification system, and the installation height of the six esterification reaction kettles in the esterification system is the same, and the reaction material is sent to the adjacent next esterification reaction through a pump at a certain flow rate. in the kettle.
具体实施方式Detailed ways
下面的实施例是对本发明的进一步阐述，但本发明不限于此。The following examples are to further illustrate the present invention, but the present invention is not limited thereto.
实施例1Example 1
将质量比例为1:2.8的PTA水池料和98％异辛醇加入到预热脱水釜中，开启机械搅拌和导热油进行升温，并保持机械搅拌下釜内温度不低于160℃，实现物料预热和脱水处理；将上述预热脱水后的反应物料由预热脱水釜通过泵(或者高位差)输送入到酯化体系中的一号酯化反应釜中，开启釜顶的催化剂计量泵，开启机械搅拌并升温进行反应；随着反应物料的连续通入，一号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵按一定流量输送到二号酯化反应釜内继续反应，随着反应进行，同理，二号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵输送到三号酯化反应釜内继续反应，随着反应进行，以此类推…，反应物料流入最后四号酯化反应釜，控制各个串联酯化反应釜中反应温度180-240℃，调控物料进入一号酯化反应釜进中的流量，使得最后四号酯化反应釜中物液酸值小于0.50mgKOH/g，反应结束的物料输送到到脱醇釜内进行连续脱醇处理。Add the PTA pool material with a mass ratio of 1:2.8 and 98% isooctanol into the preheating dehydration kettle, turn on the mechanical stirring and heat-conducting oil to heat up, and keep the temperature in the kettle not lower than 160 ℃ under the mechanical stirring to realize the material preheating. Heat and dehydration treatment; the reaction material after the above-mentioned preheating and dehydration is transported into the No. 1 esterification reaction kettle in the esterification system by the preheating dehydration kettle through a pump (or a high level difference), and the catalyst metering pump on the top of the kettle is turned on, Turn on the mechanical agitation and heat up to carry out the reaction; with the continuous introduction of the reaction material, when the reaction material in the No. 1 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the No. 2 by a pump at a certain flow rate. Continue the reaction in the No. 2 esterification reaction kettle, and as the reaction proceeds, in the same way, when the reaction material in the No. 2 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the No. 3 esterification kettle through a pump. Continue the reaction in the reaction kettle, as the reaction progresses, and so on..., the reaction material flows into the last No. 4 esterification reaction kettle. The flow rate in the kettle is such that the acid value of the material and liquid in the last fourth esterification reaction kettle is less than 0.50mgKOH/g, and the material after the reaction is transported to the dealcoholization kettle for continuous dealcoholization treatment.
表1 四号酯化反应釜中酸值随时间的变化Table 1 Variation of acid value with time in No. 4 esterification reactor
实施例2Example 2
将质量比例为1:2.6的PTA落地料和98％异辛醇加入到预热脱水釜中，开启机械搅拌和导热油进行升温，并保持机械搅拌下釜内温度不低于160℃，实现物料预热和脱水处理；将上述预热脱水后的反应物料由预热脱水釜通过泵(或者高位差)输送入到酯化体系中的一号酯化反应釜中，开启釜顶的催化剂计量泵，开启机械搅拌并升温进行反应；随着反应物料的连续通入，一号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵按一定流量输送到二号酯化反应釜内继续反应，随着反应进行，同理，二号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵输送到三号酯化反应釜内继续反应，随着反应进行，以此类推…，反应物料流入最后五号酯化反应釜，控制各个串联酯化反应釜中反应温度180-240℃，调控物料进入一号酯化反应釜进中的流量，使得最后五号酯化反应釜中物液酸值小于0.50mgKOH/g，反应结束的物料输送到到脱醇釜内进行连续脱醇处理。The mass ratio of 1:2.6 PTA floor material and 98% isooctanol were added to the preheating dehydration kettle, the mechanical stirring and heat transfer oil were turned on to heat up, and the temperature in the kettle was kept not lower than 160 ℃ under the mechanical stirring, so as to realize the material preheating. Heat and dehydration treatment; the reaction material after the above-mentioned preheating and dehydration is transported into the No. 1 esterification reaction kettle in the esterification system by the preheating dehydration kettle through a pump (or a high level difference), and the catalyst metering pump on the top of the kettle is turned on, Turn on the mechanical agitation and heat up to carry out the reaction; with the continuous introduction of the reaction material, when the reaction material in the No. 1 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the No. 2 by a pump at a certain flow rate. Continue the reaction in the No. 2 esterification reaction kettle, and as the reaction proceeds, in the same way, when the reaction material in the No. 2 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the No. 3 esterification kettle through a pump. Continue the reaction in the reaction kettle, as the reaction proceeds, and so on..., the reaction material flows into the last No. 5 esterification reaction kettle, and the reaction temperature in each serial esterification reaction kettle is controlled to 180-240 ° C, and the material is controlled to enter the No. 1 esterification reaction. The flow rate in the kettle is such that the acid value of the liquid in the last No. 5 esterification reaction kettle is less than 0.50mgKOH/g, and the material after the reaction is transported to the dealcoholization kettle for continuous dealcoholization.
表2 五号酯化反应釜中酸值随时间的变化Table 2 Variation of acid value with time in No. 5 esterification reactor
实施例3Example 3
将质量比例为1:3.2的PTA碱溶料和98％异辛醇加入到预热脱水釜中，开启机械搅拌和导热油进行升温，并保持机械搅拌下釜内温度不低于160℃，实现物料预热和脱水处理；将上述预热脱水后的反应物料由预热脱水釜通过泵(或者高位差)输送入到酯化体系中的一号酯化反应釜中，开启釜顶的催化剂计量泵，开启机械搅拌并升温进行反应；随着反应物料的连续通入，一号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵按一定流量输送到二号酯化反应釜内继续反应，随着反应进行，同理，二号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵输送到三号酯化反应釜内继续反应，随着反应进行，以此类推…，反应物料流入最后六号酯化反应釜，控制各个串联酯化反应釜中反应温度180-240℃，调控物料进入一号酯化反应釜进中的流量，使得最后六号酯化反应釜中物液酸值小于0.50mgKOH/g，反应结束的物料输送到到脱醇釜内进行连续脱醇处理。Add the PTA alkali solution material and 98% isooctanol with a mass ratio of 1:3.2 into the preheating dehydration kettle, turn on the mechanical stirring and heat transfer oil to heat up, and keep the temperature in the kettle not lower than 160 ℃ under the mechanical stirring to realize the material Preheating and dehydration treatment; the reaction material after the above-mentioned preheating and dehydration is transported into the No. 1 esterification reaction kettle in the esterification system by the preheating dehydration kettle through a pump (or a high level difference), and the catalyst metering pump on the top of the kettle is turned on. , turn on the mechanical stirring and heat up to carry out the reaction; with the continuous introduction of the reaction material, when the reaction material in the No. 1 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to a certain flow rate by a pump. Continue the reaction in the No. 2 esterification reaction kettle, and as the reaction proceeds, in the same way, when the reaction material in the No. 2 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the No. 3 ester through a pump. Continue the reaction in the reaction kettle, as the reaction progresses, and so on..., the reaction material flows into the last No. 6 esterification reaction kettle, and the reaction temperature in each series-connected esterification reaction kettle is controlled to 180-240 ° C, and the control material enters the No. 1 esterification reaction kettle. The flow rate in the reaction kettle is such that the acid value of the material and liquid in the last No. 6 esterification reaction kettle is less than 0.50mgKOH/g, and the material after the reaction is transported to the dealcoholization kettle for continuous dealcoholization treatment.
表3 六号酯化反应釜中酸值随时间的变化Table 3 Changes of acid value with time in No. 6 esterification reactor
实施例4Example 4
将质量比例为1:2.4的精对苯二甲酸和98％异辛醇加入到预热脱水釜中，开启机械搅拌和导热油进行升温，并保持机械搅拌下釜内温度不低于160℃，实现物料预热和脱水处理；将上述预热脱水后的反应物料由预热脱水釜通过泵(或者高位差)输送入到酯化体系中的一号酯化反应釜中，开启釜顶的催化剂计量泵，开启机械搅拌并升温进行反应；随着反应物料的连续通入，一号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵按一定流量输送到二号酯化反应釜内继续反应，随着反应进行，同理，二号酯化反应釜中的反应物料达到釜上部出料口时，通过管道自然溢流，或者通过泵输送到最后三号酯化反应釜内继续反应，控制各个串联酯化反应釜中反应温度180-240℃，调控物料进入一号酯化反应釜进中的流量，使得最后三号酯化反应釜中物液酸值小于0.50mgKOH/g，反应结束的物料输送到到脱醇釜内进行连续脱醇处理。Add purified terephthalic acid and 98% isooctanol with a mass ratio of 1:2.4 into the preheated dehydration kettle, turn on mechanical stirring and heat-conducting oil to heat up, and keep the temperature in the kettle not lower than 160 ℃ under mechanical stirring to achieve Material preheating and dehydration treatment; the reaction material after the above-mentioned preheating and dehydration is transported into the No. 1 esterification reaction kettle in the esterification system through a pump (or a high level difference) from the preheating dehydration kettle, and the catalyst metering at the top of the kettle is turned on. Pump, turn on the mechanical stirring and raise the temperature for the reaction; with the continuous feeding of the reaction material, when the reaction material in the No. 1 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported by the pump at a certain flow rate Continue the reaction in the No. 2 esterification reaction kettle, and as the reaction proceeds, in the same way, when the reaction material in the No. 2 esterification reaction kettle reaches the discharge port on the upper part of the kettle, it will overflow naturally through the pipeline, or be transported to the last three through the pump. Continue the reaction in the No. 1 esterification reaction kettle, control the reaction temperature in each series-connected esterification reaction kettle to 180-240 ° C, and control the flow rate of the material entering the No. 1 esterification reaction kettle, so that the final liquid acid in the No. If the value is less than 0.50mgKOH/g, the material after the reaction is transported to the dealcoholization kettle for continuous dealcoholization treatment.
表4 三号酯化反应釜中酸值随时间的变化Table 4 Variation of acid value with time in No. 3 esterification reactor
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711070334.6A CN107935846B (en) | 2017-11-03 | 2017-11-03 | Device and method for continuously producing environment-friendly plasticizer |
| NL2021197A NL2021197B1 (en) | 2017-11-03 | 2018-06-28 | A device and method for continuously producing environment-friendly plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711070334.6A CN107935846B (en) | 2017-11-03 | 2017-11-03 | Device and method for continuously producing environment-friendly plasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107935846A CN107935846A (en) | 2018-04-20 |
| CN107935846B true CN107935846B (en) | 2020-01-10 |
Family
ID=61933185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711070334.6A Active CN107935846B (en) | 2017-11-03 | 2017-11-03 | Device and method for continuously producing environment-friendly plasticizer |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107935846B (en) |
| NL (1) | NL2021197B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4023628A4 (en) * | 2020-11-17 | 2023-09-20 | LG Chem, Ltd. | Method for preparing diester-based material |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102105057B1 (en) | 2018-08-16 | 2020-04-27 | 삼성전기주식회사 | Multi-layered ceramic electronic component |
| CN109107503A (en) * | 2018-09-19 | 2019-01-01 | 长园华盛(泰兴)锂电材料有限公司 | Tandem reaction equipment of vinylene carbonate and preparation method thereof |
| KR102488351B1 (en) * | 2019-07-04 | 2023-01-13 | 주식회사 엘지화학 | Method for manufacturing diester-based material |
| CN110302737A (en) * | 2019-07-29 | 2019-10-08 | 潍坊益华化工有限公司 | A kind of continuous esterification device and process |
| CN113457571A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Polymerization inhibitor mechanism for MMA (methyl methacrylate) production device and polymerization inhibitor adding method |
| CN111732510A (en) * | 2020-07-03 | 2020-10-02 | 山东朗晖石油化学股份有限公司 | Continuous production equipment and process for DOTP plasticizer |
| CN111909037B (en) * | 2020-09-01 | 2023-04-18 | 潍坊弘润新材料有限公司 | Continuous production method of tetraisooctyl pyromellitate |
| KR102797150B1 (en) * | 2020-11-17 | 2025-04-21 | 주식회사 엘지화학 | Method for preparing diester-based material |
| KR102797134B1 (en) * | 2020-11-17 | 2025-04-21 | 주식회사 엘지화학 | Method for preparing diester compound |
| KR102797136B1 (en) * | 2020-11-17 | 2025-04-18 | 주식회사 엘지화학 | Method for preparing diester compound |
| CN112569621B (en) * | 2020-11-23 | 2021-12-03 | 湖北兴瑞硅材料有限公司 | Continuous dehydration device and dehydration process for dimethyl cyclosiloxane |
| CN112920094B (en) * | 2021-01-29 | 2024-10-18 | 江苏奥洁生物科技有限公司 | Method for regulating production load and improving yield of N-methyl sodium taurate |
| CN114933534B (en) * | 2022-04-28 | 2024-07-23 | 山东蓝帆化工有限公司 | Continuous esterification production process of diisooctyl terephthalate heterogeneous system |
| CN115010633B (en) * | 2022-07-11 | 2024-04-12 | 宁夏汉润生物科技有限公司 | Synthesis method and device of ring-closing compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503831A (en) * | 2011-11-07 | 2012-06-20 | 潍坊市元利化工有限公司 | Continuous esterification production method for plasticizer |
| CN104496819A (en) * | 2014-12-17 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing environment-friendly plasticizer by recycling waste resources |
-
2017
- 2017-11-03 CN CN201711070334.6A patent/CN107935846B/en active Active
-
2018
- 2018-06-28 NL NL2021197A patent/NL2021197B1/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503831A (en) * | 2011-11-07 | 2012-06-20 | 潍坊市元利化工有限公司 | Continuous esterification production method for plasticizer |
| CN104496819A (en) * | 2014-12-17 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | Method for preparing environment-friendly plasticizer by recycling waste resources |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4023628A4 (en) * | 2020-11-17 | 2023-09-20 | LG Chem, Ltd. | Method for preparing diester-based material |
| US12275698B2 (en) | 2020-11-17 | 2025-04-15 | Lg Chem, Ltd. | Method of preparing diester-based material |
Also Published As
| Publication number | Publication date |
|---|---|
| NL2021197B1 (en) | 2019-01-15 |
| CN107935846A (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107935846B (en) | Device and method for continuously producing environment-friendly plasticizer | |
| CN103242164B (en) | Continuous preparation process for environment-friendly plasticizer and device used in process | |
| CN103044257B (en) | Terylene waste material produces alcoholysis method and the apparatus system of dioctyl terephthalate | |
| CN104098762B (en) | Bottle grade PET device and production technique thereof | |
| CN105001091A (en) | Esterification reaction process for plasticizer DOTP (dioctyl terephthalate) | |
| CN101891620B (en) | Continuous esterification production method of di-sec-octyl phthalate | |
| CN111889059A (en) | A kind of reaction device and process for preparing DOTP | |
| CN206372821U (en) | A kind of device for producing DOTP | |
| CN107814709A (en) | A kind of high-quality glycolic purifying technique | |
| CN101139290A (en) | Esterification reaction-pervaporation membrane separation integrated process method for producing vitamin C | |
| CN113318677A (en) | DOTP production device and process | |
| CN216972385U (en) | A kind of continuous esterification production device of diisooctyl terephthalate | |
| CN102161718B (en) | Method and device for continuously producing chlorinated polyvinyl chloride by low-temperature plasma circulating bed | |
| CN204897793U (en) | DOTP plasticizer esterification reaction device | |
| CN205188176U (en) | Di n butyl phthalate plasticizer esterification reaction system | |
| CN114768278B (en) | DOTP continuous production device and production process thereof | |
| CN204079855U (en) | A kind of bottle grade PET device | |
| CN105732363A (en) | Method for preparing gluconic acid by taking glucose as raw material under different working conditions | |
| CN207143010U (en) | The dehydration device of esterification products under a kind of acid condition | |
| CN210434521U (en) | Esterification reaction device of polyester | |
| CN104230706A (en) | Preparation method of pentaerythritol oleate | |
| CN114933534B (en) | Continuous esterification production process of diisooctyl terephthalate heterogeneous system | |
| CN203095920U (en) | Device for producing epoxy fatty acid methyl ester | |
| CN201670810U (en) | A device for synthesizing dibasic carboxylic acid esters with multiple reactors in series for continuous deep esterification | |
| CN107382725A (en) | A kind of method of continuous production dihydroxy acetic acid MENTHOL ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |