WO2021196383A1 - Px生产pta的外置微界面机组强化反应***及工艺 - Google Patents
Px生产pta的外置微界面机组强化反应***及工艺 Download PDFInfo
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- 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
- B01J19/0053—Details of the reactor
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- 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
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- 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
- B01J19/24—Stationary reactors without moving elements inside
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- the present invention relates to the technical field of chemical engineering, in particular to an enhanced reaction system and process of an external micro-interface unit for PX production of PTA.
- TA terephthalic acid
- PX para-xylene
- acetic acid is used as solvent
- cobalt acetate, manganese acetate and hydrobromic acid are used as catalysts.
- TA terephthalic acid
- PX p-xylene
- TALD p-tolualdehyde
- p-TA p-toluic acid
- 4-CBA p-carboxybenzaldehyde
- the four oxidation reaction steps in the PX oxidation process are all carried out in the same reactor.
- the first two reaction steps need to use acetic acid as the solvent, and high temperature and high pressure are not suitable.
- the prior art adopts a mixed reaction process. , Without giving different conditions for different reactions, the acetic acid consumption is large, the energy consumption is high, and accompanied by a large number of side reactions, the impurity content is high, and the product quality cannot be guaranteed.
- the present invention proposes an intensified reaction system and process for an external micro-interface unit for PX production of PTA, which aims to solve the problem of large consumption of acetic acid and high energy consumption in the existing PX production of PTA, accompanied by a large number of side reactions. , High impurity content, product quality cannot be guaranteed.
- the present invention provides an enhanced reaction system of an external micro-interface unit for PX production of PTA, which includes a reactor, a first micro-interface generator and a second micro-interface generator; wherein,
- the reactor includes a shell, a feed port, a first baffle plate, a second baffle plate, and a circulating heat exchange device partially arranged outside the shell. Both sides of the first baffle plate are connected to the On the inner side wall of the reactor, the height of the top end of the first baffle plate is lower than the height of the liquid level of the reactor, and the position of the bottom end of the first baffle plate is higher than the position of the feed inlet; Both sides of the two baffle plates are connected to the inner side wall of the reactor, the top height of the second baffle plate is lower than or equal to the top height of the first baffle plate, and the second baffle plate The position of the bottom end is higher than the position of the feed inlet, and the bottom end of the second baffle plate is closed and connected to the inner side wall of the housing;
- a first reaction zone is formed between the inner wall of one side of the housing and the first baffle plate, and a first overflow zone is formed between the first baffle plate and the second baffle plate.
- An overflow zone is in communication with the first reaction zone, a second overflow zone is formed between the second baffle plate and the inner wall of the other side of the shell, and the bottom of the reactor is the second reaction zone;
- the reaction material in the first reaction zone overflows into the first overflow zone, wherein the catalyst particles fall into the first overflow zone under the action of their own gravity, and the catalyst particles are removed from the first overflow zone.
- the reaction material in the first overflow zone overflows into the second overflow zone.
- the first micro-interface generator is respectively connected with the feed port and the circulating heat exchange device, the second micro-interface generator is arranged at the bottom of the second reaction zone, and the first micro-interface generator Both the second micro-interface generator are used to break the raw material air into micro-bubbles.
- the first reaction zone is to convert p-xylene into p-tolualdehyde, p-tolualdehyde into p-toluic acid, A reaction zone for converting p-toluic acid into p-carboxybenzaldehyde, and the second reaction zone is a reaction zone for converting p-carboxybenzaldehyde into terephthalic acid.
- the bottom of the first baffle plate has a bend, and the bend angle is bent in the direction of the second baffle plate to prevent reaction
- the upward rush of the airflow at the bottom of the device prevents solid particles from falling into the first overflow zone.
- the first micro-interface generator and the second micro-interface generator are both pneumatic micro-interface generators.
- At least one circulating pump is provided on the circulating heat exchange device.
- a first anti-wave grid and a second anti-wave grid are arranged inside the reactor, and the first anti-wave grid is arranged The position is lower than the height of the top of the first baffle plate, and the position of the second anti-wave grille is lower than the position of the feed inlet.
- a filter screen is also arranged above the inside of the reactor to prevent impurities inside the first reaction zone from entering the top of the reactor.
- the top of the reactor is provided with a tail gas outlet, and the bottom of the reactor is provided with a product outlet.
- the present invention also proposes an enhanced reaction process of an external micro-interface unit for PX production of PTA, which is characterized in that it includes the following steps:
- the mixture of p-xylene, acetic acid and catalyst is passed into the first micro-interface generator, and at the same time, the air is broken into micro-bubbles through the first micro-interface generator, and the mixture is fully mixed and emulsified and then enters the first reaction zone for pairing.
- the reaction materials in the reaction process pass through the first anti-wave grid, wherein the catalyst particles fall into the first overflow zone under the action of their own gravity to remove the catalyst.
- the reaction material in the first overflow zone overflows into the second overflow zone, and the reaction material in the second overflow zone enters the circulating pipe of the circulating heat exchange device to form a circulating stream,
- the circulating stream is used to control the temperature during the reaction process;
- the p-carboxybenzaldehyde generated in the first reaction zone enters the second reaction zone through the second anti-wave grid.
- the air is broken into microbubbles from the second micro-interface generator and then enters the second reaction zone.
- Carboxybenzaldehyde undergoes oxidation reaction to generate terephthalic acid.
- the temperature of the reactor is 160-190° C.
- the pressure is 0.62-2.25 MP.
- the present invention has the following beneficial effects:
- the enhanced reaction system and process of the external micro-interface unit for PX production by PX adopts a segmented reaction process, and the inside of the reactor is set as the first reaction zone, the second reaction zone, the first overflow zone and the second reaction zone.
- the two overflow zones realize different reaction conditions for different reaction stages in the same reactor, solve the problem that the acetic acid solvent cannot withstand high temperature and pressure in the first two reaction steps, and use water as the solvent for the p-TA oxidation reaction. It effectively solves the problems of large consumption of acetic acid and high energy consumption in the prior art, accompanied by a large number of side reactions, high impurity content, and product quality cannot be guaranteed.
- the external micro-interface unit for PX production of PTA provided by the present invention strengthens the reaction system and process.
- a micro-interface generator at the feed port and the bottom of the reactor, the air is broken to break it into microbubbles, and The liquid phase material forms an emulsion, which effectively increases the mass transfer area between the air and the liquid phase material, reduces the thickness of the liquid film, and reduces the mass transfer resistance, thereby effectively reducing energy consumption and improving reaction efficiency.
- the external micro-interface unit for PX production of PTA strengthens the reaction system and process.
- the temperature in the reaction process is effectively controlled during the reaction process, and the inside of the reactor is ensured at the same time.
- the uniformity of the mixing of the reaction materials ensures that the reactants can fully participate in the reaction, thereby greatly improving the utilization rate of the reactants, and at the same time preventing the occurrence of side reactions caused by local temperature unevenness, to a certain extent Improve the quality of the product.
- FIG. 1 is a schematic structural diagram of an enhanced reaction system of an external micro-interface unit for PX production of PTA provided by an embodiment of the present invention.
- 10 is the shell
- 11 is the first reaction zone
- 12 is the second reaction zone
- 13 is the first baffle plate
- 14 is the second baffle plate
- 15 is the first overflow zone
- 16 is the second overflow Flow area
- 17 is the first micro-interface generator
- 18 is the second micro-interface generator
- 19 is the first anti-wave grid
- 20 is the second anti-wave grid
- 21 is the filter screen
- 22 is the feed inlet .
- an enhanced reaction system of an external micro-interface unit for PX production of PTA includes: a reactor, a first micro-interface generator 17 and a second micro-interface generator 18;
- the device includes: a housing 10, a feed port 22, a first baffle plate 13, a second baffle plate 14 and a circulating heat exchange device partially arranged outside the housing 10.
- the two sides of the first baffle plate 13 are connected On the inner side wall of the reactor, the height of the top end of the first partition plate 13 is lower than the height of the liquid level of the reactor, and the position of the bottom end of the first partition plate 13 is higher than the inlet material 21 Position; the two sides of the second partition plate 14 are connected to the inner side wall of the reactor, and the height of the top end of the second partition plate 14 is lower than or equal to the height of the top end of the first partition plate 13 The position of the bottom end of the second partition plate 14 is higher than the position of the inlet 22, and the bottom end of the second partition plate 14 is closed and connected to the inner side wall of the housing 10;
- the first reaction zone 11 Between the inner wall of one side of the housing 10 and the first partition plate 13 is the first reaction zone 11, and the first reaction zone 11 is used for converting para-xylene into para-tolualdehyde and para-toluene.
- the first overflow zone 15 is in communication with the first reaction zone 11; between the second partition plate 14 and the other inner wall of the housing 10 is a second overflow zone 16, and the reaction
- the bottom of the vessel is a second reactor 12, and the second reaction zone 12 is a reaction zone where the p-carboxybenzaldehyde is converted to terephthalic acid.
- the reaction material in the first reaction zone 11 overflows into the first overflow zone 15, and the reaction material in the first overflow zone 15 after removing solid particles overflows into the second overflow zone.
- the overflow zone 16; the liquid phase stream in the second overflow zone 16 forms a circulating stream through the circulating pipe on the circulating heat exchange device, and the circulating stream is used to effectively control the reaction process during the reaction process.
- it ensures the uniformity of mixing between the reactant streams in the reactor, and ensures that each reactant can fully participate in the reaction, thereby greatly improving the utilization of the reactants, and preventing the occurrence of side reactions caused by uneven local temperature. , Improve the quality of products to a certain extent.
- the top of the reactor is also provided with a tail gas outlet.
- the tail gas includes acetic acid and water.
- the tail gas enters the subsequent tail gas processing unit, and the separated acetic acid can be recycled and reused, which saves the cost of the enterprise.
- the bottom of the reactor is also provided with a product outlet, which is used to take out the reaction product terephthalic acid and unreacted p-xylene PX, solvent, catalyst and by-products, etc., and finally the reaction product enters the subsequent separation and refining section.
- a staged reaction process is adopted, and the inside of the reactor is arranged as the first reaction zone, the second reaction zone, the first overflow zone and the second overflow zone, so that the reactor can be used in the same reactor.
- Different reaction conditions are given for different reaction stages in the internal, which solves the problem that the acetic acid solvent cannot withstand high temperature and pressure in the first two reaction steps, and uses water as the solvent for the p-TA oxidation reaction, which effectively solves the consumption of acetic acid in the prior art Large, high energy consumption, accompanied by a large number of side reactions, high impurity content, and product quality cannot be guaranteed.
- the first micro-interface generator 17 is respectively connected to the feed port 22 and the circulating heat exchange device
- the second micro-interface generator 18 is arranged at the bottom of the second reaction zone 12
- Both the second micro-interface generator and the second micro-interface generator 18 are pneumatic micro-interface generators, which are used to break the air into micro-bubbles before entering the inside of the reactor, and form an emulsion with the liquid-phase materials, effectively increasing the air and liquid-phase materials.
- the mass transfer area between them reduces the thickness of the liquid film and reduces the mass transfer resistance, thereby effectively reducing energy consumption and improving reaction efficiency.
- micro-interface generator The specific structure of the micro-interface generator is embodied in the inventor's previous patents, such as the patent of publication number 106215730A.
- the core of the micro-interface generator is bubble breakage, which will not be repeated here.
- reaction mechanism and control method of the micro-interface generator it has been disclosed in the previous patent CN107563051B of the present inventor, which will not be repeated here.
- the micro-interface generator is arranged in each reaction zone inside the reactor, and the air is broken in each reaction zone to break it into micro-bubbles and form an emulsion with the liquid phase material, which is effective
- the ground increases the mass transfer area between the air and the liquid phase material, reduces the thickness of the liquid film, and reduces the mass transfer resistance, thereby effectively reducing energy consumption and improving reaction efficiency.
- At least one circulating pump is provided on the circulating heat exchange device of the reactor, and the number of the circulating pumps is not specifically required, and can be added at the corresponding position as required.
- the installation of multiple circulating pumps can increase the circulating power, making the heat exchange efficiency higher and the heat exchange more uniform.
- the inside of the reactor is also provided with a first wave-breaking grid 19 and a second wave-breaking grid 20, and the first wave-breaking grid 19 is arranged at a position lower than that of the first baffle 13
- the height of the top of the second wave grid 20 is lower than the position of the feed inlet 22, and the first wave grid 19 is used to convert the violent full mixed flow in the upper part of the first reaction zone 11 into a horizontal push After the flow, overflow is performed to prevent solid particles from entering the second overflow zone 16; the second wave grid 20 is used to convert the fully mixed flow in the first reaction zone 11 into a horizontal plug flow and then enter the second reaction zone 12.
- a filter screen 21 is also provided above the inside of the reactor to prevent impurities in the first reaction zone 11 from entering the top of the reactor and affecting subsequent tail gas treatment.
- the raw material mixture including p-xylene, acetic acid, and catalysts enter the first micro-interface generator 17, and at the same time, pass air into the first micro-interface generator 17 to break It is mixed with the raw material mixture and emulsified, which effectively increases the contact area between the air and the liquid phase reaction material.
- the emulsified liquid enters the first reaction zone 11 for the first three steps of reaction, that is, p-xylene is converted into p-xylene.
- Methylbenzaldehyde and p-tolualdehyde are converted into p-toluic acid, and p-toluic acid is converted into p-carboxybenzaldehyde.
- the unreacted air leaves the liquid surface and passes through the filter screen 21 and rises to the top of the reactor. ;
- the reaction materials in the reaction process pass through the first anti-wave grid 19, wherein the solid particles fall into the first overflow zone 15 under the action of their own gravity.
- the p-carboxybenzaldehyde generated in the first reaction zone 11 enters the second reaction zone 12 through the second anti-wave grill 20 provided at the bottom of the reactor, and the air is broken into microbubbles from the second micro-interface generator 18 and then enters the first In the second reaction zone 12, the oxidation reaction with the p-carboxybenzaldehyde produces terephthalic acid as a product.
- the staged reaction process is adopted in the present invention, and the inside of the reactor is arranged as the first reaction zone, the second reaction zone, the first overflow zone and the second overflow zone, so as to achieve the same
- Different reaction conditions are given to different reaction stages in the reactor, which solves the problem that the acetic acid solvent cannot withstand high temperature and high pressure in the first two reaction steps, and uses water as the solvent for the p-TA oxidation reaction, which effectively solves the problem of acetic acid in the prior art.
- Large consumption, high energy consumption, accompanied by a large number of side reactions, high impurity content, and product quality cannot be guaranteed.
- the air is broken into micro-bubbles, which form an emulsion with the liquid-phase materials, effectively increasing the gap between the air and the liquid-phase materials.
- the mass transfer area is reduced, the thickness of the liquid film is reduced, and the mass transfer resistance is reduced, thereby effectively reducing energy consumption and improving reaction efficiency.
- the temperature in the reaction process is effectively controlled during the reaction process, while ensuring the uniformity of the mixing of the reaction materials in the reactor, and ensuring that the reactants can fully participate
- the reaction greatly improves the utilization rate of the reactants, and at the same time prevents the occurrence of side reactions caused by uneven local temperature, and improves the quality of the product to a certain extent.
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Abstract
一种PX生产PTA的外置微界面机组强化反应***及工艺,包括:反应器、第一微界面发生器(17)和第二微界面发生器(18);其中,反应器包括外壳(10)、进料口(22)、第一隔挡板(13)、第二隔挡板(14)以及部分设置在外壳(10)外部的循环换热装置;外壳(10)的一侧内壁与第一隔挡板(13)之间为第一反应区(11),第一隔挡板(13)和第二隔挡板(14)之间为第一溢流区(15),第一溢流区(15)与第一反应区(11)连通;第二隔挡板(14)和外壳(10)的另一侧内壁之间为第二溢流区(16),反应器的底部为第二反应区(12);第一微界面发生器(17)分别与进料口(22)和循环换热装置连接,第二微界面发生器(18)设置在第二反应区(12)底部,第一微界面发生器(17)和第二微界面发生器(18)均用以将原料空气破碎为微气泡。
Description
本发明涉及化工技术领域,具体而言,涉及一种PX生产PTA的外置微界面机组强化反应***及工艺。
TA(对苯二甲酸)是一种重要的化工原料,一般以PX(对二甲苯)为原料,以醋酸为溶剂,以醋酸钴、醋酸锰和氢溴酸(或四溴甲烷)为催化剂,在一定的温度和压力下,利用空气中的氧气氧化制得TA(对苯二甲酸),主要包括4个步骤,对二甲苯(PX)→对甲基苯甲醛(TALD)→对甲基苯甲酸(p-TA)→对羧基苯甲醛(4-CBA)→对苯二甲酸(TA),其中4个步骤均是不可逆反应,反应过程非常复杂。
现有技术中,PX氧化过程中的四个氧化反应步骤均在同一个反应器中进行,,然而前两个反应步骤要以醋酸为溶剂,不宜采用高温高压,现有技术采用混合的反应工艺,没有针对不同的反应给予不同的条件,使得醋酸消耗量大,能耗高,同时伴随着大量的副反应,杂质含量高,产品质量无法得到保证。
发明内容
鉴于此,本发明提出了一种PX生产PTA的外置微界面机组强化反应***及工艺,旨在解决现有的PX生产PTA过程中醋酸消耗量大,能耗高,同时伴随着大量副反应,杂质含量高,产品质量无法得到保证的问题。
一个方面,本发明提出了一种PX生产PTA的外置微界面机组强化反应***,包括反应器、第一微界面发生器和第二微界面发生器;其中,
所述反应器包括外壳、进料口、第一隔档板、第二隔档板以及部分设置在 所述外壳外部的循环换热装置,所述第一隔档板的两侧连接在所述反应器的内侧壁上、所述第一隔档板的顶端高度低于所述反应器液面高度、所述第一隔档板的底端位置高于所述进料口位置;所述第二隔档板的两侧连接在所述反应器的内侧壁上、所述第二隔档板的顶端高度低于或等于所述第一隔档板的顶端高度、所述第二隔档板的底端位置高于所述进料口位置、所述第二隔档板的底端封闭连接在所述外壳的内侧壁上;
所述外壳的一侧内壁与所述第一隔档板之间为第一反应区,所述第一隔档板和所述第二隔档板之间为第一溢流区,所述第一溢流区与所述第一反应区连通,所述第二隔档板和所述外壳的另一侧内壁之间为第二溢流区,所述反应器的底部为第二反应区;反应过程中,所述第一反应区的反应物料溢流进所述第一溢流区中,其中,催化剂颗粒在自身重力的作用下落入所述第一溢流区中,除去催化剂颗粒后的所述第一溢流区的反应物料溢流进所述第二溢流区中。
所述第一微界面发生器分别与所述进料口和所述循环换热装置连接,所述第二微界面发生器设置在所述第二反应区底部,所述第一微界面发生器和所述第二微界面发生器均用以将原料空气破碎为微气泡。
进一步地,上述PX生产PTA的外置微界面机组强化反应***中,所述第一反应区为进行对二甲苯转化为对甲基苯甲醛、对甲基苯甲醛转化为对甲基苯甲酸、对甲基苯甲酸转化为对羧基苯甲醛的反应区,所述第二反应区为所述对羧基苯甲醛转化为对苯二甲酸的反应区。
进一步地,上述PX生产PTA的外置微界面机组强化反应***中,所述第一隔档板的底部具有弯角,所述弯角向所述第二隔档板方向弯折,以防止反应器底部气流上冲阻止固体颗粒落入所述第一溢流区。
进一步地,上述PX生产PTA的外置微界面机组强化反应***中,所述第一微界面发生器和所述第二微界面发生器均为气动式微界面发生器。
进一步地,上述PX生产PTA的外置微界面机组强化反应***中,所述循环换热装置上设置有至少一个循环泵。
进一步地,上述PX生产PTA的外置微界面机组强化反应***中,所述反应器的内部设置有第一防浪格栅和第二防浪格栅,所述第一防浪格栅设置的位置低于所述第一隔档板的顶端高度,所述第二防浪格栅设置的位置低于所述进料口位置。
进一步地,上述PX生产PTA的外置微界面机组强化反应***中,所述反应器的内部上方还设置有除滤网,用以防止所述第一反应区内部的杂质进入反应器的顶部。
进一步的,上述PX生产PTA的外置微界面机组强化反应***中,所述反应器的顶部设置有尾气出口,所述反应器的底部设置有产物出口。
另一方面,本发明还提出了一种PX生产PTA的外置微界面机组强化反应工艺,其特征在于,包括如下步骤:
将对二甲苯、醋酸和催化剂的混合物通入第一微界面发生器中,同时将空气通过第一微界面发生器内破碎成微气泡,与混合物充分混合乳化后进入第一反应区内进行对二甲苯转化为对甲基苯甲醛、对甲基苯甲醛转化为对甲基苯甲酸、对甲基苯甲酸转化为对羧基苯甲醛的反应,未反应完的所述空气离开液面上升到反应器的上方;
随着第一反应区内上述反应的不断进行,反应过程中的反应物料穿过第一防浪格栅,其中,催化剂颗粒在自身重力的作用下落入所述第一溢流区中,除去催化剂颗粒后的所述第一溢流区的反应物料溢流进所述第二溢流区中,所述第二溢流区的反应物料进入所述循环换热装置的循环管道内形成循环物流,所述循环物流用以控制反应过程中的温度;
第一反应区内生成的对羧基苯甲醛通过第二防浪格栅进入第二反应区中,空气从第二微界面发生器中破碎成微气泡后进入第二反应区中,与所述对羧基苯甲醛进行氧化反应生成对苯二甲酸。
进一步地,上述PX生产PTA的外置微界面机组强化反应工艺中,所述反应器温度为160-190℃,压强为0.62-2.25MP。
与现有技术相比,本发明的有益效果在于:
本发明提供的PX生产PTA的外置微界面机组强化反应***及工艺,采用分段式的反应工艺,将反应器内部设置为第一反应区、第二反应区、第一溢流区和第二溢流区,实现了在同一反应器内针对不同反应阶段给予不同反应条件,解决了前两部反应步骤中醋酸溶剂不能承受高温高压的问题,并且利用水作为p-TA氧化反应的溶剂,有效地解决了现有技术中醋酸消耗量大,能耗高,同时伴随着大量副反应,杂质含量高,产品质量无法得到保证的问题。
进一步的,本发明提供的PX生产PTA的外置微界面机组强化反应***及工艺,通过在进料口和反应器底部设置微界面发生器,对空气进行破碎,使其破碎为微气泡,与液相物料形成乳化液,有效地增大了空气与液相物料之间的传质面积,减小液膜厚度,降低传质阻力,进而有效地降低了能耗、提升了反应效率。
进一步的,本发明提供的PX生产PTA的外置微界面机组强化反应***及工艺,通过设置循环换热装置,在反应进行的过程中有效控制了反应过程中的温度,同时确保了反应器内部各反应物料之间混合的均匀度,确保了各反应物能够充分的参与反应,进而极大地提升了反应物的利用率,同时防止了因局部温度不均引发副反应的发生,在一定程度上提升了产物的质量。
通过阅读下文优选实施方式的详细描述,各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的,而并不认为是对本发明的限制。而且在整个附图中,用相同的参考符号表示相同的部件。在附图中:
图1为本发明实施例提供的PX生产PTA的外置微界面机组强化反应***的结构示意图。
图中:10为外壳、11为第一反应区、12为第二反应区、13为第一隔档板、 14为第二隔档板、15为第一溢流区、16为第二溢流区、17为第一微界面发生器、18为第二微界面发生器、19为第一防浪格栅、20为第二防浪格栅、21为除滤网、22为进料口。
下面将参照附图更详细地描述本公开的示例性实施例。虽然附图中显示了本公开的示例性实施例,然而应当理解,可以以各种形式实现本公开而不应被这里阐述的实施例所限制。相反,提供这些实施例是为了能够更透彻地理解本公开,并且能够将本公开的范围完整的传达给本领域的技术人员。需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
参阅图1所示,为本发明实施例的PX生产PTA的外置微界面机组强化反应***,其包括:反应器、第一微界面发生器17和第二微界面发生器18;其中,反应器包括:外壳10、进料口22、第一隔档板13、第二隔档板14以及部分设置在外壳10外部的循环换热装置,所述第一个隔挡板13的两侧连接在所述反应器的内侧壁上、所述第一隔挡板13的顶端高度低于所述反应器液面高度、所述第一隔挡板13的底端位置高于所述进口料21位置;所述第二隔挡板14的两侧连接在所述反应器的内侧壁上、所述第二隔挡板14的顶端高度低于或等于所述第一隔挡板13的顶端高度、所述第二隔挡板14的底端位置高于所述进料口22位置、所述第二隔挡板14的底端封闭连接在所述外壳10的内侧壁上;
所述外壳10的一侧内壁与所述第一隔挡板13之间为第一反应区11,所述第一反应区11为进行对二甲苯转化为对甲基苯甲醛、对甲基苯甲醛转化为对甲基苯甲酸、对甲基苯甲酸转化为对羧基苯甲醛的反应区,所述第一隔挡板13和所述第二隔挡板14之间为第一溢流区15,所述第一溢流区15与所述第一反应区11连通;所述第二隔挡板14和所述外壳10的另一侧内壁之间为第二溢 流区16,所述反应器的底部为第二反应器12,所述第二反应区12为所述对羧基苯甲醛转化为对苯二甲酸的反应区。反应过程中,所述第一反应区11的反应物料溢流进所述第一溢流区15中,除去固体颗粒后的所述第一溢流区15的反应物料溢流进所述第二溢流区16中;所述第二溢流区16中的液相物流通过循环换热装置上的循环管道形成一个循环物流,所述循环物流用以在反应过程中有效地控制反应过程中的温度,同时确保反应器内部各反应物流之间混合的均匀度,确保各反应物能够充分的参与反应,进而极大的提升反应物的利用率,同时防止因局部温度不均引发副反应的发生,在一定程度上提升产物的质量。
此外,反应器顶端还开设有尾气出口,所述尾气包括醋酸和水,所述尾气进入后续尾气处理单元中,分离出的醋酸可以重复循环利用,节约了企业成本。反应器底部还开设有产物出口,用于取出反应产物对苯二甲酸和未反应完的对二甲苯PX、溶剂、催化剂以及副产物等,最后将反应产物进入后续分离精制工段。
可以理解的是,本发明中采用分段式的反应工艺,将反应器内部设置为第一反应区、第二反应区、第一溢流区和第二溢流区,实现了在同一反应器内针对不同反应阶段给予不同反应条件,解决了前两部反应步骤中醋酸溶剂不能承受高温高压的问题,并且利用水作为p-TA氧化反应的溶剂,有效地解决了现有技术中醋酸消耗量大,能耗高,同时伴随着大量副反应,杂质含量高,产品质量无法得到保证的问题。
本实施例中,第一微界面发生器17分别与进料口22和循环换热装置连接,第二微界面发生器18设置在第二反应区12底部,所述第一微界面发生器17和所述第二微界面发生器18均为气动式微界面发生器,用以将空气进入反应器内部前破碎为微气泡,与液相物料形成乳化液,有效地增大了空气与液相物料之间的传质面积,减小液膜厚度,降低传质阻力,进而有效的降低了能耗、提升了反应效率。关于微界面发生器的具体构造在本发明人在先专利中体现,如公开号106215730A的专利,微界面发生器其核心在于气泡破碎,此不再赘 述。关于微界面发生器的反应机理及控制方法,在本发明人在先专利CN107563051B中已经公开,此不再赘述。可以理解的是,本发明中通过在反应器内部的各个反应区内设置微界面发生器,在各反应区内部对空气进行破碎,使其破碎为微气泡,与液相物料形成乳化液,有效地增大了空气与液相物料之间的传质面积,减小液膜厚度,降低传质阻力,进而有效地降低了能耗、提升了反应效率。
优选的,反应器的循环换热装置上设置有至少一个循环泵,所述循环泵的个数没有具体要求,可以根据需要加在相应的位置。加装多个循环泵可增加循环动力,使得换热效率更高,换热更均匀。
本实施例中,所述反应器的内部还设置有第一防浪格栅19和第二防浪格栅20,所述第一防浪格栅19设置的位置低于第一隔挡板13的顶端高度,所述第二防浪格栅20设置的位置低于所述进料口22位置,第一防浪格栅19用以将第一反应区11上部剧烈的全混流转化为平推流后再进行溢流,防止固体颗粒进入第二溢流区16;第二防浪格栅20用以将第一反应区11的全混流转化为平推流后进入第二反应区12。
本实施例中,反应器的内部上方还设置有除滤网21,用以防止所述第一反应区11内部的杂质进入反应器的顶部,影响后续尾气处理。
请结合图1所示,本实施例PX生产PTA的外置微界面机组强化反应***的工作过程为:
首先,原料混合物包括对二甲苯、醋酸和催化剂(醋酸钴、醋酸锰、氢溴酸)等进入到第一微界面发生器17中,同时,将空气通入第一微界面发生器17中破碎成微气泡,与原料混合物混合乳化,有效的增大了空气与液相反应物料之间的接触面积,乳化液进入到第一反应区11内部进行前三步反应,即对二甲苯转化为对甲基苯甲醛、对甲基苯甲醛转化为对甲基苯甲酸、对甲基苯甲酸转化为对羧基苯甲醛,未反应完的空气离开液面穿过除滤网21上升到反应器的上方;
随着第一反应区11内上述反应的不断进行,反应过程中的反应物料穿过第一防浪格栅19,其中,固体颗粒在自身重力的作用下落入所述第一溢流区15中,除去固体颗粒后的所述第一溢流区15的反应物料溢流进所述第二溢流区16中,所述第二溢流区16的反应物料进入所述循环换热装置的循环管道内形成循环物流,所述循环物流用以控制反应过程中的温度;
第一反应区11内生成的对羧基苯甲醛通过反应器底部设置的第二防浪格栅20进入第二反应区12中,空气从第二微界面发生器18中破碎成微气泡后进入第二反应区12中,与所述对羧基苯甲醛进行氧化反应生成产物对苯二甲酸。
显然可以得出的是,本发明中采用分段式的反应工艺,将反应器内部设置为第一反应区、第二反应区、第一溢流区和第二溢流区,实现了在同一反应器内针对不同反应阶段给予不同反应条件,解决了前两部反应步骤中醋酸溶剂不能承受高温高压的问题,并且利用水作为p-TA氧化反应的溶剂,有效地解决了现有技术中醋酸消耗量大,能耗高,同时伴随着大量副反应,杂质含量高,产品质量无法得到保证的问题。
进一步的,通过在进料口和反应器底部设置微界面发生器,对空气进行破碎,使其破碎为微气泡,与液相物料形成乳化液,有效地增大了空气与液相物料之间的传质面积,减小液膜厚度,降低传质阻力,进而有效地降低了能耗、提升了反应效率。
进一步的,通过设置循环换热装置,在反应进行的过程中有效控制了反应过程中的温度,同时确保了反应器内部各反应物料之间混合的均匀度,确保了各反应物能够充分的参与反应,进而极大地提升了反应物的利用率,同时防止了因局部温度不均引发副反应的发生,在一定程度上提升了产物的质量。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包含这些改动和变型在内。
Claims (10)
- 一种PX生产PTA的外置微界面机组强化反应***,其特征在于,包括:反应器、第一微界面发生器和第二微界面发生器;其中,所述反应器包括外壳、进料口、第一隔档板、第二隔档板以及部分设置在所述外壳外部的循环换热装置,所述第一隔档板的两侧连接在所述反应器的内侧壁上、所述第一隔档板的顶端高度低于所述反应器液面高度、所述第一隔档板的底端位置高于所述进料口位置;所述第二隔档板的两侧连接在所述反应器的内侧壁上、所述第二隔档板的顶端高度低于或等于所述第一隔档板的顶端高度、所述第二隔档板的底端位置高于所述进料口位置、所述第二隔档板的底端封闭连接在所述外壳的内侧壁上;所述外壳的一侧内壁与所述第一隔档板之间为第一反应区,所述第一隔档板和所述第二隔档板之间为第一溢流区,所述第一溢流区与所述第一反应区连通;所述第二隔档板和所述外壳的另一侧内壁之间为第二溢流区,所述反应器的底部为第二反应区;反应过程中,所述第一反应区的反应物料溢流进所述第一溢流区中,其中,固体颗粒在自身重力的作用下落入所述第一溢流区中,除去固体颗粒后的所述第一溢流区的反应物料溢流进所述第二溢流区中;所述第一微界面发生器分别与所述进料口和所述循环换热装置连接,所述第二微界面发生器设置在所述第二反应区底部,所述第一微界面发生器和所述第二微界面发生器均用以将原料空气破碎为微气泡。
- 根据权利要求1所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述第一反应区为进行对二甲苯转化为对甲基苯甲醛、对甲基苯甲醛转化为对甲基苯甲酸、对甲基苯甲酸转化为对羧基苯甲醛的反应区,所述第二反应区为所述对羧基苯甲醛转化为对苯二甲酸的反应区。
- 根据权利要求1所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述第一隔档板的底部具有弯角,所述弯角向所述第二隔档板方向弯折,以防止反应器底部气流上冲阻止固体颗粒落入所述第一溢流区。
- 根据权利要求1所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述第一微界面发生器和所述第二微界面发生器均为气动式微界面发生器。
- 根据权利要求1所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述循环换热装置上设置有至少一个循环泵。
- 根据权利要求1-5任一项所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述反应器的内部设置有第一防浪格栅和第二防浪格栅,所述第一防浪格栅设置的位置低于所述第一隔档板的顶端高度,所述第二防浪格栅设置的位置低于所述进料口位置。
- 根据权利要求1-5任一项所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述反应器的内部上方还设置有除滤网,用以防止所述第一反应区内部的杂质进入反应器的顶部。
- 根据权利要求1-5任一项所述的PX生产PTA的外置微界面机组强化反应***,其特征在于,所述反应器的顶部设置有尾气出口,所述反应器的底部设置有产物出口。
- 一种PX生产PTA的外置微界面机组强化反应工艺,其特征在于,包括如下步骤:将对二甲苯、醋酸和催化剂的混合物通入第一微界面发生器中,同时将空气通过第一微界面发生器内破碎成微气泡,与混合物充分混合乳化后进入第一反应区内进行对二甲苯转化为对甲基苯甲醛、对甲基苯甲醛转化为对甲基苯甲酸、对甲基苯甲酸转化为对羧基苯甲醛的反应,未反应完的所述空气离开液面上升到反应器的上方;随着第一反应区内上述反应的不断进行,反应过程中的反应物料穿过第一防浪格栅,其中,催化剂颗粒在自身重力的作用下落入所述第一溢流区中,除去催化剂颗粒后的所述第一溢流区的反应物料溢流进所述第二溢流区中,所述第二溢流区的反应物料进入所述循环换热装置的循环管道内形成循环物流,所 述循环物流用以控制反应过程中的温度;第一反应区内生成的对羧基苯甲醛通过第二防浪格栅进入第二反应区中,空气从第二微界面发生器中破碎成微气泡后进入第二反应区中,与所述对羧基苯甲醛进行氧化反应生成对苯二甲酸。
- 根据权利要求9所述的所述PX生产PTA的外置微界面机组强化反应工艺,其特征在于,所述反应器温度为160-190℃,压强为0.62-2.25MPa。
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CN1528732A (zh) * | 2003-10-12 | 2004-09-15 | 浙江大学 | 一种生产对苯二甲酸用的鼓泡塔氧化反应装置 |
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CN205222790U (zh) * | 2015-09-29 | 2016-05-11 | 中石化炼化工程(集团)股份有限公司 | 气升式三相环流床反应器 |
CN106237966A (zh) * | 2016-08-23 | 2016-12-21 | 南京大学 | 用于甲苯类物质氧化生产芳香醛的反应器 |
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