CN114984888B - Circulation reactor system for continuous esterification for producing plasticizer - Google Patents
Circulation reactor system for continuous esterification for producing plasticizer Download PDFInfo
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- CN114984888B CN114984888B CN202210470491.0A CN202210470491A CN114984888B CN 114984888 B CN114984888 B CN 114984888B CN 202210470491 A CN202210470491 A CN 202210470491A CN 114984888 B CN114984888 B CN 114984888B
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 222
- 230000032050 esterification Effects 0.000 title claims abstract description 51
- 239000004014 plasticizer Substances 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 239000002002 slurry Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000005191 phase separation Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 24
- 238000003860 storage Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000005192 partition Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 16
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000010924 continuous production Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000007273 lactonization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
Abstract
The invention discloses a circulating reactor system for producing continuous esterification of plasticizer, which comprises a continuous reaction unit, a slurry configuration unit, a gas phase separation unit and a buffer tank, wherein the slurry configuration unit, the gas phase separation unit and the buffer tank are respectively connected with the continuous reaction unit; the continuous reaction unit comprises two first esterification reaction kettles and a second esterification reaction kettle which are arranged in series, the slurry configuration unit is connected with the first esterification reaction kettle, and reaction materials enter the first esterification reaction kettle and the second esterification reaction kettle to react after entering the slurry configuration system for configuration, and finally enter the buffer tank; the gas phase separation unit is respectively connected with the first esterification reaction kettle and the second esterification reaction kettle and forms a gas phase circulation system. By adopting the technical scheme, the esterification reaction kettle is divided into a plurality of reaction sections, so that continuous esterification reaction is realized, and the method can be used for large-scale continuous industrial production.
Description
Technical Field
The invention belongs to the technical field of plasticizer production, and relates to a circulating reactor system for continuous esterification for producing plasticizers.
Background
The plasticizer is added for increasing the plasticity and fluidity of the polymer such as rubber, plastic, paint and the like and enabling the finished product to have flexibility when the polymer is molded, and is an essential additive aid for the plastic industry, wherein the proportion of phthalate and terephthalate occupies more than 90 percent, but researches show that the phthalate plasticizer has potential carcinogenicity, and the green plasticizers such as epoxy grease, citrate and the like are difficult to meet huge market demands in short term in terms of yield, so that the demands of the plasticizer in the future are also quite large. However, the traditional synthesis process has long time consumption and high energy consumption, the traditional plasticizer production adopts esterification intermittent feeding, and the subsequent system continuous production process has the problems of complicated operation, high energy consumption, low yield and the like. The batch esterification method is characterized in that an acid or anhydride required by the reaction, excessive alcohol and a catalyst are added into an esterification reaction kettle according to a certain proportion in a batch feeding mode, the esterification reaction is carried out by heating, the esterification material is transferred to the next process for treatment after reaching the end of the reaction, the empty esterification reaction kettle continues the esterification reaction of the next batch, that is, the reaction material is required to be manually transferred after the lactonization reaction of the esterification reaction kettle is finished, and the continuous operation cannot be carried out. The method is long in production time, meanwhile, due to the fact that the intermittent esterification process adopted in the production process is influenced by various superposition factors, the quality of products among production batches is unstable, certain differences exist in the performance parameters of products in different batches, the energy consumption is high, the yield is low, and large-scale production cannot be achieved.
Chinese patent No. CN102503831a provides a continuous esterification process for producing plasticizer, which provides at least two continuous esterification reactors connected in series and provided with catalyst reaction beds, the temperature of each continuous esterification reactor is raised in sequence, superheated alcohol gas is continuously introduced into each continuous esterification reactor, countercurrent reaction is carried out on the pre-esterification material and the catalyst reaction beds, and plasticizer products are continuously extracted from the bottom of the terminal continuous esterification reactor. The esterification reaction of the continuous esterification reactors connected in series is maintained by introducing overheated pure steam into the reactors, however, in actual reaction, the alcohol steam in the reactors is always in an excessive state, the excessive alcohol steam and the water steam in each stage of the reactors are discharged out of the reactors together, so that the insufficient alcohol in the reactors of the next stage cannot continue the next reaction, and excessive alcohol steam needs to be introduced again into the continuous esterification reactors of each stage to maintain the reaction, which leads to huge waste of reaction raw materials, and a treatment device with operation procedures not containing the hot alcohol is added. Chinese patent CN203474763U discloses a continuous transesterification reactor and apparatus, in which the transesterification reactor disclosed in the patent is the most commonly used reactor in the prior art, materials enter from the bottom of the transesterification reactor, and the materials are fully mixed and reacted by stirring during the rising process of the transesterification reactor, and the residence time is calculated according to the reaction time, and the volume is calculated according to the residence time, so as to ensure continuous reaction and achieve the purpose of continuous production. When the reactor is utilized, on one hand, in order to continuously run materials upwards, the stirring speed needs to be increased, so that the materials continuously move upwards and overflow to the previous cavity from the cavity opening, the phenomenon of deposition at the bottom of the reactor is avoided, when the reaction is in a high-speed running state, the gas-phase materials in the high-temperature state are seriously evaporated, a large amount of alcohol phase is lost, and therefore, higher alkyd ratio is needed, the energy consumption is high, and the raw material consumption is high; on the other hand, when the materials are in a state in the stirring process, the movement of the materials can occur and the same frequency can not be realized, so that the proportion of the materials of the reaction system in the cavity of each section of reaction is not equal, and the reaction yield is low.
Disclosure of Invention
The invention aims to provide a circulating reactor system for producing plasticizer for continuous esterification, which can realize continuous reaction, reduce the alkyd ratio in esterification and save energy.
In order to achieve the above object, the present invention provides a circulation reactor system for continuous esterification for producing plasticizer, comprising a continuous reaction unit, a slurry configuration unit, a gas phase separation unit and a buffer tank, which are respectively connected with the continuous reaction unit; the continuous reaction unit comprises two first esterification reaction kettles and a second esterification reaction kettle which are arranged in series, the slurry configuration unit is connected with the first esterification reaction kettle, and reaction materials enter the first esterification reaction kettle and the second esterification reaction kettle to react after entering the slurry configuration system for configuration, and finally enter the buffer tank; the gas phase separation unit is respectively connected with the first esterification reaction kettle and the second esterification reaction kettle and forms a gas phase circulation system.
Further, the second esterification reaction kettle is horizontally placed, a plurality of partition boards are arranged in the vertical direction in the second esterification reaction kettle, and the second esterification reaction kettle is divided into a plurality of communicated reaction sections; the length of the partition plate is smaller than the diameter of the second esterification reaction kettle, so that the second esterification reaction kettle is communicated; and a stirrer is arranged in each reaction section, esterification reaction is carried out in each reaction section, and the reaction section passes through the last section and then is discharged out of the second esterification reaction kettle to enter the buffer tank.
Further, the baffle at least bottom fixed set up in the inner wall of second esterification reaction cauldron, open-ended makes all the top of reaction section is linked together, thereby makes the reaction material pass through the last level in proper order the reaction section gets into the next level the reaction section.
Further, the height of the partition plate is 1/2-2/3 of the diameter of the second esterification reaction kettle.
Further, the first esterification reaction kettle and the second esterification reaction kettle are both provided with stirrers; the stirrer comprises a stirring motor, a stirring shaft and stirring blades, wherein the stirring shaft is connected with the stirring motor and is arranged in the esterification reaction kettle from top to bottom, the stirring blades are arranged on the stirring shaft, and the rotation speed of the stirring blades is adjusted through the stirring motor; the stirring blade is fixedly provided with a catalyst storage box, the outer wall of the catalyst storage box is provided with a filter hole, and along with the rotation of the stirring blade, the catalyst is discharged out of the catalyst storage box through the filter hole and enters the esterification reaction kettle.
Further, a filter membrane is arranged at the bottom of the first esterification reaction kettle; the first esterification reaction kettle adopts steam tracing, and steam tracing adopts a steam tracing pipe to heat, and the steam tracing pipe is spirally wound on the inner wall of the first esterification reaction kettle, so that the inner wall of the whole kettle is guaranteed to be heated uniformly.
Further, the slurry preparation unit comprises a high-level storage tank, a slurry preparation kettle and a slurry finished product kettle, wherein the slurry preparation kettle is respectively connected with the high-level storage tank and the slurry finished product kettle, and each reaction raw material is respectively input into the slurry preparation kettle through the high-level storage tank according to a required proportion, premixed and then input into the slurry finished product kettle for pulping to form a uniformly dispersed slurry system.
Further, slurry mixers are arranged in the slurry finished product kettles, so that the slurry system is kept in a uniform dispersion state, and caking is prevented.
Further, gas phase generated by the first esterification reaction kettle and/or the second esterification reaction kettle enters the gas phase circulation system, is separated by the gas phase separation unit, and then returns to the first esterification reaction kettle and/or the second esterification reaction kettle again for recycling; the gas phase separation unit comprises a fractionating tower, a dephlegmator, a condenser and a reflux tank; the fractionating tower is connected with the second esterification reaction kettle; the dephlegmator is arranged at the top of the fractionating tower, and the dephlegmator and the fractionating tower are coupled; the dephlegmator, the condenser, the reflux tank and the dephlegmator are sequentially connected to form a circulating separation system, gas phase enters the dephlegmator through the fractionating tower, and after the gas phase enters the circulating separation system for multiple times, the alcohol phase returns to the fractionating tower for reuse.
Further, the circulating separation system is provided with a reflux pump, and the reflux pump, the fractionating tower and the dephlegmator are respectively provided with regulating valves, so that an alcohol phase in the circulating separation system is input into the gas-phase circulating system or the circulating separation system.
The invention adopts a horizontal esterification reaction kettle, the esterification reaction kettle is divided into a plurality of reaction sections, and a stirrer is arranged in each reaction section, so that the reaction materials in the reaction sections overflow upwards and flow into the next reaction section to carry out esterification reaction, thereby realizing continuous esterification reaction.
By applying the technical scheme, compared with the prior art, the invention has the following advantages:
1. the technical scheme of the invention adopts a circulating reactor system, wherein a horizontal esterification reaction kettle is divided into a plurality of reaction sections, so that esterification reaction is respectively carried out in each reaction section, the esterification rate is improved, and continuous esterification reaction is realized; meanwhile, the alcohol phase in the esterification reaction section is evaporated to a circulation system to be circulated and returned to the esterification reaction kettle so as to supplement the requirement of alcohol in the esterification reaction and ensure the forward progress of the esterification reaction, so that the invention can be used for large-scale continuous industrial production; meanwhile, the plasticizer obtained after esterification is discharged into a buffer tank, each batch is not required to be subjected to refining and purifying procedures, and the continuous operation of the esterification reaction kettle is realized through centralized one-time treatment after a plurality of batches.
2. By adopting the technical scheme of the invention, based on the gas-phase circulation system and the circulation reactor system of the circulation separation system, the esterification reaction kettle can timely discharge the generated alcohol water vapor so as to be beneficial to maintaining the reaction temperature in the esterification reaction kettle and keeping the continuous progress of the esterification reaction; meanwhile, alcohol and water vapor are returned to the reaction system through a circulation system after being separated in time, so that the alcohol in the reaction system is kept in an excessive state, the forward direction of the esterification reaction is ensured, and the continuous esterification reaction is realized.
3. According to the technical scheme, materials enter the second esterification reaction kettle from the bottom of the first esterification reaction kettle, the reaction materials are fully mixed and react in the feeding process in the second esterification reaction kettle, the residence time is calculated according to the reaction time, and the volume is calculated according to the residence time, so that continuous reaction is ensured, and the purpose of continuous production is achieved.
4. By adopting the technical scheme of the invention, the partition plate can adopt a detachable structure, the number and the space size of the reaction sections can be adjusted according to the needs, and the partition plate is convenient to clean and overhaul.
5. Compared with the traditional intermittent esterification, the technical scheme of the invention can reduce the labor intensity of workers and improve the stability of the production process and the product quality.
Drawings
Fig. 1 is a schematic structural diagram of a slurry configuration unit according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of the structure of a continuous reaction unit according to an embodiment of the present invention.
FIG. 3 is a schematic diagram showing the structure of a gas phase separation unit according to an embodiment of the present invention.
Wherein, the reference numerals in the figures are respectively: preparing a kettle 1 from slurry; a second reactant feed inlet 101; premix stirrer 102; a high-level storage tank 2; a first reactant feed input port 201; a slurry finished product kettle 3; slurry stirrer 301; a slurry transfer pump 4; a first esterification reaction vessel 5; a first esterification mixer 501; a first gas phase outlet 502; a second esterification reaction vessel 6; a partition 601; second esterification agitator 602; a second gas phase outlet 603; a buffer tank 7; a fractionating tower 8; a gas phase input 801; a dephlegmator 9; a liquid return pipe 901; a condenser 10; a pressure control valve 1001; a reflux drum 11; a reflow system 12; a first return pump 1201; a second return pump 1202.
Detailed Description
The invention provides a circulating reactor system for producing continuous esterification of plasticizer, which comprises a continuous reaction unit, a slurry configuration unit, a gas phase separation unit and a buffer tank, wherein the slurry configuration unit, the gas phase separation unit and the buffer tank are respectively connected with the continuous reaction unit; the continuous reaction unit comprises two first esterification reaction kettles and a second esterification reaction kettle which are arranged in series, the slurry configuration unit is connected with the first esterification reaction kettle, and reaction materials enter the first esterification reaction kettle and the second esterification reaction kettle to react after entering the slurry configuration system for configuration, and finally enter the buffer tank; the gas phase separation unit is respectively connected with the first esterification reaction kettle and the second esterification reaction kettle to form a gas phase circulation system.
The esterification reaction kettle can timely discharge generated alcohol water vapor so as to maintain the reaction temperature in the esterification reaction kettle to maintain the continuous progress of the esterification reaction; and meanwhile, the alcohol steam is timely separated and then returned to the reaction system by a circulating system, so that the alcohol in the reaction system is kept in an excessive state, and the forward progress of the esterification reaction is ensured.
And the crude product obtained after the reaction in the second esterification reaction kettle enters a buffer tank, and the product is refined after the crude product obtained by continuous production and preparation for multiple times is accumulated, so that the refining cost is saved.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention in conjunction with the specific contents of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Specifically, referring to fig. 1, the slurry configuration unit of the present embodiment includes a high-level tank 2, a slurry configuration tank 1, a slurry product tank 3, a slurry transfer pump 4, and two material input ports. The slurry preparation kettle 1 is respectively connected with a high-level storage tank 2 and a slurry finished product kettle 3, and the slurry preparation kettle 3 is connected with a slurry conveying pump 4. The material input ports are a first reaction material input port 201 and a second reaction material input port 101 respectively, the first reaction material input port 201 is connected with the high-level storage tank 2, the second reaction material input port 101 is connected with the slurry preparation kettle 1, acid or anhydride is input into the high-level storage tank 2 through the first reaction material input port 201, and alcohol input by the second reaction material input port 101 enters the slurry preparation kettle 1 together according to a required proportion for premixing; the premixed mixed material is conveyed into a slurry finished product kettle 3 through a communicating pipeline for mixing and pulping to obtain mixed slurry, and the mixed slurry is conveyed into a continuous reaction unit through a slurry conveying pump 4 for continuous esterification reaction.
Further, the slurry preparation kettle 1 and the slurry finished product kettle 3 are both provided with mechanical stirring, the mechanical stirring in the slurry preparation kettle 1 is respectively a premixing stirrer 102, and a slurry stirrer 301 arranged in the slurry finished product kettle 3 keeps a slurry system in the kettle in a uniformly dispersed state and prevents caking.
Preferably, the slurry stirrer 301 comprises a stirring shaft and a plurality of layers of stirring paddles fixedly mounted on the stirring shaft, wherein each layer of stirring paddles consists of 3 columnar paddles, and the included angle between the stirring shaft and the paddles is 70-90 degrees. The stirring paddle structure adopting the structure aims to increase the stirring uniformity.
Referring to fig. 2, a continuous reaction unit in this embodiment includes two first esterification reaction kettles 5, a second esterification reaction kettle 6 and a buffer tank 7, in which a slurry transfer pump 4 in a slurry configuration unit is connected with the first esterification reaction kettle 5, and after a reaction material enters a slurry configuration system to be configured into slurry, the slurry is sequentially fed into the first esterification reaction kettle 5 and the second esterification reaction kettle 6 via the slurry transfer pump 4 to perform an esterification reaction. The buffer tank 7 is connected with the discharge port of the second esterification reaction kettle 6, the plasticizer crude product obtained after esterification is discharged into the buffer tank 7, and concentrated refining treatment is performed after continuous production of a plurality of batches, so that the times of refining operation procedures are reduced. The bottom of the first esterification reaction kettle 5 is provided with a discharge opening, the discharge opening is connected with a feed inlet arranged at the bottom of the second esterification reaction kettle 6, and the first esterification reaction kettle 5 inputs the reaction material subjected to pre-esterification into the second esterification reaction kettle 6 through the discharge opening.
The first esterification reaction kettle 5 and the second esterification reaction kettle 6 are internally provided with a temperature controller and a pressure controller, and the outside is provided with a temperature display and a pressure display to keep the stability of the reaction temperature.
The first esterification reaction kettle 5 comprises a first gas phase outlet 502, the second esterification reaction kettle 6 comprises a second gas phase outlet 603, the gas phase separation units are respectively connected with the first gas phase outlet 502 and the second gas phase outlet 603 to enable the first esterification reaction kettle 5, the second esterification reaction kettle 6 and the gas phase separation units to form a gas phase circulation system, gas phases of an alcohol-water azeotropic system generated in the kettles are respectively discharged through the first gas phase outlet 502 and the second gas phase outlet 603 and enter the gas phase separation units, and after alcohol-water separation, the alcohol phase can return to the kettles in an original way to participate in the esterification reaction.
The first esterification reaction kettle 5 is provided with a filter membrane at the bottom of the reaction kettle and is provided with a first esterification stirrer 501. The filter membrane is arranged at least at the discharge opening of the first esterification reaction kettle 5, so that the catalyst is prevented from entering the second esterification reaction kettle 6 along with the materials, and the catalyst is kept in the first esterification reaction kettle 5 to the greatest extent. Preferably, the catalyst selected in this embodiment is a molecular sieve solid catalyst.
The first esterification reaction kettle 5 uses steam heat tracing to ensure that the whole kettle is heated uniformly. The steam tracing adopts a pipeline heating mode of a steam tracing pipe to be uniformly laid on the inner wall of the first esterification reaction kettle 5. Preferably, the steam accompanying pipe is spirally wound on the inner wall of the first esterification reaction kettle 5.
The second esterification reaction kettle 6 is a horizontal reaction kettle which is horizontally placed, a plurality of baffle plates 601 are arranged in the vertical direction, and the second esterification reaction kettle 6 is divided into a plurality of communicated reaction sections to form a multi-stage reaction area; the height of the baffle 601 is smaller than the diameter of the inner wall of the second esterification reaction kettle, so that all reaction sections in the second esterification reaction kettle 6 are communicated; and a second esterification stirring stirrer 602 is arranged in each reaction section, the reaction materials sequentially perform esterification reaction in each reaction section, and the reaction materials are discharged out of the second esterification reaction kettle after passing through the last reaction section and enter a buffer tank 7.
Preferably, at least the bottom end of the partition 601 is fixedly disposed on the inner wall of the second esterification reaction kettle, and the top end of the partition is opened, so that the tops of all the reaction sections are communicated, and the reaction materials can sequentially pass through the reaction section of the previous stage and enter the reaction section of the next stage. In the high-speed stirring process of the second esterification stirrer 602 in the reaction section, the reaction materials circularly flow in the reaction area of the reaction section, and along with the continuous input of the reaction materials, the materials circulated to the top end enter the next-stage reaction section through the upper end opening of the baffle 601 to continue the esterification reaction, so that the first-stage and the second-stage are transferred to the next-stage reaction section. Preferably, the number of the partition plates is 3 to 6, that is, the inside of the second esterification reaction vessel is divided into 3 to 6 reaction sections. The feed inlet of the second esterification reaction kettle 6 is positioned at the bottom of the first-stage reaction section, and the discharge outlet of the second esterification reaction kettle 6 is positioned at the bottom of the last-stage reaction section.
It is further preferable that the height of the partition plate is 1/2 to 2/3 of the inner diameter of the second esterification reactor 6.
First esterification mixer 501 and second esterification mixer 602 are both mechanical mixers, and may have the same structure, or may have the same structure as slurry mixer 301.
As a preferred embodiment, the first esterification stirrer 501 and the second esterification stirrer 602 are both provided with stirring blades, a catalyst storage box is fixedly arranged on the stirring blades, a filter hole is arranged on the outer wall of the catalyst storage box, and along with the rotation of the stirring blades, the catalyst is discharged out of the catalyst storage box through the filter hole and enters the second esterification reaction kettle. In the first esterification reaction vessel 5, at the start of the esterification reaction, the catalyst is added into the catalyst storage box according to the ratio, and as stirring proceeds, the catalyst enters the reaction system, and since the catalyst is always retained in the first esterification reaction vessel 5, the catalyst may not need to be replenished.
The catalyst in the second esterification reaction kettle 6 is discharged along with the reaction materials, and the catalyst in the catalyst storage box can be added in an on-line supplementary way according to the circulation speed of the materials. Preferably, the catalyst storage box is provided with a catalyst adding pipeline for replenishing the catalyst at any time.
As a preferred embodiment, the stirrer of first esterification stirrer 501 and/or second esterification stirrer 602 comprises a stirring motor, a stirring shaft and stirring blades, wherein the stirring shaft is connected with the stirring motor and is arranged in the esterification reaction kettle from top to bottom, the stirring blades are arranged on the stirring shaft, and the rotation speed of the stirring blades is adjusted by the stirring motor.
Referring to fig. 3, a gas phase separation unit of the present embodiment includes a fractionation column 8, a dephlegmator 9, a condenser 10, and a reflux drum 11. The fractionating tower 8 is provided with a gas phase input end 801 which is connected with the second esterification reaction kettle 6; the dephlegmator 9 is arranged at the top of the fractionating tower 8, and the dephlegmator 9 and the dephlegmator are connected to form a coupling structure, so that bidirectional flow can be carried out, and gas phase directly enters through the internal channels of the fractionating tower 8 and the dephlegmator 9. The inner wall of the dephlegmator 9 is provided with condensate water circulation, and the gas is partially condensed in the dephlegmator and then flows back into the fractionating tower 8 through the liquid return pipe 901.
The dephlegmator 9, the condenser 10, the reflux tank 11 and the dephlegmator 9 are sequentially connected to form a circulating separation system, and gas phase enters the dephlegmator 9 through the fractionating tower 8, so that after entering the circulating separation system for circulation, alcohol phase returns to the fractionating tower 8 and can enter the continuous reaction unit again to participate in esterification reaction, and recycling is realized.
In the circulating separation system, the water vapor and the alcohol vapor are subjected to alcohol-water separation by an alcohol-water separation device (a reflux tank 11) after passing through a condensing device (a dephlegmator 9 and a condenser 10), the alcohol phase forms reflux alcohol which returns to participate in the esterification reaction, and the water phase is discharged out of the circulating separation system through the reflux tank 11. A pressure control valve 1001 is provided between the dephlegmator 9 and the condenser 10 to regulate the pressure entering the condenser 10.
Preferably, a reflux system 12 is provided between reflux drum 11 and dephlegmator 9, reflux system 12 comprising two first reflux pump 1201 and second reflux pump 1202 arranged in parallel to deliver the alcohol phase to fractionation column 8 or dephlegmator 9, respectively.
The operating steps for carrying out the production of the continuous esterification of plasticizer using this example include: (1) raw material conveying: inputting acid or anhydride into the high-level storage tank 2 through the first reaction material input end 201, and entering the slurry preparation kettle 1 together with alcohol input through the second reaction material input end 101 for premixing; the premixed material is conveyed into a slurry finished product kettle 3 through a communicating pipeline for mixed pulping; (2) continuous esterification: the mixed material is conveyed into a first esterification reaction kettle 5 through a slurry conveying pump 4; under the action of a catalyst, the reaction materials are sequentially subjected to esterification reaction in a first esterification reaction kettle 5 and a second esterification reaction kettle 6 which are connected in series, the reacted materials sequentially pass through the esterification reaction kettle of the previous stage and then enter the esterification reaction kettle of the next stage, the esterification reaction is sequentially carried out in a reaction section in the second esterification reaction kettle 6, and the products are discharged into a buffer tank 7; (3) recycling the alcohol phase: the alcohol-water azeotropic system generated in the first esterification reaction kettle 5 and the second esterification reaction kettle 6 is discharged into the fractionating tower 8 through a gas phase outlet of the esterification reaction kettle, the alcohol phase and the water phase are separated through the circulating separation system and then are recycled back into the fractionating tower again to be returned into the esterification reaction kettle for continuous participation in the esterification reaction, and excessive alcohol is recycled to form a circulating system with a multi-stage structure, so that the temperature and pressure conditions in the esterification reaction kettle are kept in a range for promoting the forward direction of the esterification reaction system; meanwhile, the excess alcohol can be fully utilized, the alcohol phase is continuously circulated between the gas state and the liquid state, the alcohol-acid ratio is reduced, and the esterification rate is improved.
Alcohol vapor and water vapor generated in the esterification reaction kettle are respectively condensed in a fractionating tower 8-condenser 9 connected with the first esterification reaction kettle 5 and the second esterification reaction kettle 6, and then sequentially enter a condenser 10-reflux tank 11 for sedimentation separation of alcohol and water; wherein the alcohol phase is fed to the fractionating tower 8 or the condenser 9 through the reflux pump 1201, and is used as reflux alcohol or enters the circulating separation system again, and the water phase is discharged to the water storage tank 13.
By adopting the technical scheme of the invention, the esterification rate in the first esterification reaction kettle 5 is ensured to reach more than 90 percent, and the esterification rate can reach more than 99.9 percent after the step-by-step esterification reaction of the second esterification reaction kettle 6.
As a preferable embodiment, the continuous esterification unit in the invention can be used for increasing the number of esterification reaction kettles connected in series according to actual production requirements, so that the production efficiency and the esterification rate are improved.
The reaction system can divide the esterification reaction into a plurality of reaction sections for gradual reaction, thereby realizing the continuity of the reaction, being different from the intermittent esterification process in the prior art, having simple operation and reduced energy consumption, and further reducing the operation and production cost.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A circulating reactor system for producing continuous esterification of plasticizer, which is characterized by comprising a continuous reaction unit, a slurry configuration unit, a gas phase separation unit and a buffer tank, wherein the slurry configuration unit, the gas phase separation unit and the buffer tank are respectively connected with the continuous reaction unit;
the continuous reaction unit comprises two first esterification reaction kettles and a second esterification reaction kettle which are arranged in series, the slurry configuration unit is connected with the first esterification reaction kettle, and reaction materials enter the first esterification reaction kettle and the second esterification reaction kettle to react after entering the slurry configuration unit for configuration, and finally enter the buffer tank;
the gas phase separation unit is respectively connected with the first esterification reaction kettle and the second esterification reaction kettle and forms a gas phase circulation system;
the second esterification reaction kettle is a horizontal reaction kettle which is horizontally placed, and a plurality of baffle plates are arranged in the vertical direction to divide the second esterification reaction kettle into a plurality of communicated reaction sections; the height of the partition plate is smaller than the inner diameter of the second esterification reaction kettle, so that the second esterification reaction kettle is communicated; a stirrer is arranged in each reaction section, esterification reaction is sequentially carried out in each reaction section, and the reaction section passes through the last section and then is discharged out of the second esterification reaction kettle to enter the buffer tank;
the first esterification reaction kettle is provided with a filter membrane at the bottom of the reaction kettle;
the gas phase generated by the first esterification reaction kettle and/or the second esterification reaction kettle enters the gas phase circulation system, is separated by the gas phase separation unit, and then returns to the first esterification reaction kettle and/or the second esterification reaction kettle again for recycling;
the gas phase separation unit comprises a fractionating tower, a dephlegmator, a condenser and a reflux tank; the fractionating tower is connected with the second esterification reaction kettle; the dephlegmator is arranged at the top of the fractionating tower, and the dephlegmator and the fractionating tower are coupled; the dephlegmator, the condenser, the reflux tank and the dephlegmator are sequentially connected to form a circulating separation system, gas phase enters the dephlegmator through the fractionating tower, and after the gas phase enters the circulating separation system for multiple times, the alcohol phase returns to the fractionating tower for reuse;
in the circulating separation system, water vapor and alcohol vapor enter a reflux tank to realize alcohol-water separation after passing through a dephlegmator and a condenser, alcohol phase forms reflux alcohol to return to participate in esterification reaction, water phase is discharged out of the circulating separation system through the reflux tank, a pressure control valve is arranged between the dephlegmator and the condenser, and the pressure entering the condenser is regulated;
the bottom end of the partition plate is fixedly arranged on the inner wall of the second esterification reaction kettle, and the top end of the partition plate is open, so that the tops of all the reaction sections are communicated, and the reaction materials can sequentially enter the reaction section of the next stage through the reaction section of the previous stage;
the circulating separation system is provided with a reflux pump, and the reflux pump is respectively provided with a regulating valve with the fractionating tower and the dephlegmator, so that an alcohol phase in the circulating separation system is input into the gas-phase circulating system or the circulating separation system.
2. The circulating reactor system for continuous esterification for producing plasticizer according to claim 1, wherein the height of the partition plate is 1/2 to 2/3 of the diameter of the second esterification reactor.
3. The circulating reactor system for continuous esterification production of plasticizers according to claim 1, characterized in that the first esterification reaction vessel and the second esterification reaction vessel are each provided with a stirrer; the stirrer comprises a stirring motor, a stirring shaft and stirring blades, wherein the stirring shaft is connected with the stirring motor and is arranged in the esterification reaction kettle from top to bottom, the stirring blades are arranged on the stirring shaft, and the rotation speed of the stirring blades is adjusted through the stirring motor; the stirring blade is fixedly provided with a catalyst storage box, the outer wall of the catalyst storage box is provided with a filter hole, and along with the rotation of the stirring blade, the catalyst is discharged out of the catalyst storage box through the filter hole and enters the esterification reaction kettle.
4. The circulating reactor system for continuous esterification for producing plasticizer according to claim 1, wherein the slurry preparing unit comprises a high-level storage tank, a slurry preparing kettle and a slurry finished product kettle, the slurry preparing kettle is respectively connected with the high-level storage tank and the slurry finished product kettle, and each reaction raw material is respectively input into the slurry preparing kettle according to a required proportion through the high-level storage tank, premixed and then input into the slurry finished product kettle for pulping, so as to form a uniformly dispersed slurry system.
5. The circulating reactor system for continuous esterification for producing plasticizer according to claim 4, wherein slurry agitators are provided in the slurry finishing tanks to maintain the slurry system in a uniformly dispersed state and prevent caking.
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Inventor after: Xi Zhenhao Inventor after: Li Pei Inventor after: Liu Yanhua Inventor after: Zhao Ling Inventor after: Jiang Jie Inventor after: Li Mingdong Inventor after: Song Fangjun Inventor after: Li Jinjin Inventor after: Sun Changchun Inventor after: Chen Lizhen Inventor before: Xi Zhenhao Inventor before: Li Pei Inventor before: Liu Yanhua Inventor before: Zhao Ling Inventor before: Jiang Jie Inventor before: Li Mingdong Inventor before: Song Wanjun Inventor before: Li Jinjin Inventor before: Sun Changchun Inventor before: Chen Lizhen |