CN115572274B - Method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as raw material - Google Patents
Method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as raw material Download PDFInfo
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Abstract
The invention belongs to the field of organic chemistry, and particularly relates to a method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as a raw material. Adding cracking carbon V from the lower part of the continuous reactor, adding maleic anhydride particles from the top of the continuous reactor, reacting cyclopentadiene in the cracking carbon V with the maleic anhydride particles, and precipitating the generated solid-phase nadic anhydride to the bottom of the continuous reactor; the incompletely reacted cracked carbon five liquid phase flows out from an overflow port at the upper part of the continuous reactor; pumping the incompletely reacted cracked carbon five liquid phase and the maleic anhydride in a molten state into a microchannel reactor for reaction to obtain the methyl tetrahydrophthalic anhydride. The invention changes the traditional reaction mode for preparing solid nadic anhydride, and the essence of the reaction mode is that the two raw materials react in opposite movement. The invention realizes continuous reaction by the reaction mode that the maleic anhydride particles move downwards under the influence of gravity and the cracking carbon moves upwards, and is great progress in the field.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as a raw material.
Background
Cis-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (NA) is also called cis-5-norbornene-2,3-dicarboxylic anhydride or nadic anhydride, and is an important chemical raw material widely used in the aspects of resins, pesticides, medicines and the like. Methyl tetrahydrophthalic anhydride (MTHPA), also known as methyl tetrahydrophthalic anhydride, is an important industrial raw material and is widely applied to the industries of electronics, medicines and the like.
Cracking C5 is a byproduct in an ethylene cracking process, wherein the mass fraction of cyclopentadiene, isoprene and trans-1,3-pentadiene accounts for 40-55% of the total amount (Zhang Zhaohao. The comprehensive utilization status and development prospect of cracking C5 is in short-line [ J ] light engineering technology, 2020,36 (01): 28-29). China has low utilization rate of isoprene, and the consumption amount per year is less than 1 percent of the yield. With the change of the automobile power structure in China, the domestic demand for cracking C5 is further enlarged.
The reaction of cracking cyclopentadiene, isoprene and maleic anhydride to generate anhydride curing agent is Diels-Alder reaction, which belongs to strong exothermic reaction, and the reaction in the traditional kettle type reactor easily causes local uneven heating, and easily causes self-polymerization of diene and low product quality caused by local high temperature. The microchannel reactor has high heat transfer and mass transfer efficiency, and the specific surface area of heat transfer can reach 10-50 times of that of the traditional tank reactor (Liquid-Liquid flow in a capillary micro reactor: dynamic flow patterns and reaction performance [ J ]. Industrial & Engineering Chemistry Research,2011, 51 (2): 1015.). The microchannel reactor has the characteristics of no amplification effect, high integration degree and green process (the application of the microreactor in the field of chemical engineering [ J ]. The chemical engineering progress, 2016,35 (01): 10-17) and has very wide development prospect.
Chinese patent CN102127039A discloses a preparation method of exo-type nadic anhydride, which comprises gradually adding maleic anhydride into mixed carbon five, stirring, controlling the reaction temperature at 0~5 ℃, stopping the reaction when no cyclopentadiene is detected by gas chromatography, centrifugally separating, vaporizing, compressing and condensing liquid to obtain acyclic carbon five, wherein the solid is endo-type nadic anhydride; then, taking endo-nadic anhydride as a raw material, short-chain alcohol as a solvent, urotropine, benzoyl peroxide and [ Cu (dppm) (NO) 3 )] 2 Performing reflux reaction for 10 to 24h as a catalyst, filtering to remove the catalyst, recovering the solvent under reduced pressure, and crystallizing the mixed solvent of toluene and acetone to obtain the external Nadic anhydride; the main components of the mixed carbon five are cyclopentadiene, isoprene and piperylene; the main components of the acyclic carbon five are isoprene and piperylene. The patent uses a batch kettle type reactor, so that continuous production of nadic anhydride cannot be realized, the method only has one-time use of raw materials, a single product and insufficient utilization of the raw materials, particularly of mixed carbon-penta-m-pentadiene and isoprene, and cannot achieve the purpose of co-production of methyl tetrahydrophthalic anhydride.
Chinese patent CN109824639A discloses methyltetrahydrophthalic anhydride and a preparation method thereof, wherein carbon five and a polymerization inhibitor are put into a reaction kettle, the temperature in the kettle is raised to 45 to 50 ℃, and the pressure in the kettle is adjusted to 0.06 to 0.095MPa; dripping maleic anhydride into the reaction kettle, controlling the temperature in the kettle to be 45-80 ℃ in the dripping process, keeping the temperature in the kettle to be 45-80 ℃, and keeping the temperature for 1-2h; then reducing the pressure in the kettle to 50 to 60kPa, heating to 100 to 120 ℃, and evaporating the residual unreacted carbon five and the polymerization inhibitor to obtain a crude product; adding an alkaline catalyst into the crude product, heating to 160-170 ℃, preserving heat for 2-3 h, and distilling under reduced pressure to obtain the methyltetrahydrophthalic anhydride. The kettle reactor used in the patent has the defects of low heat transfer and mass transfer efficiency and long reaction time; in addition, a polymerization inhibitor is introduced in the patent to relieve the olefin self-polymerization reaction caused by local high temperature in the tank reactor, and the introduced polymerization inhibitor as an impurity may have some influence on the purity of the product.
The two methods disclosed by the Chinese patent CN102127039A and the Chinese patent CN109824639A are both batch-type reaction, and continuous production cannot be realized.
Disclosure of Invention
The invention aims to provide a method for coproducing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as a raw material, which can reduce the production cost, improve the utilization rate of the raw material and safely and efficiently continuously produce nadic anhydride and methyl tetrahydrophthalic anhydride.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the invention relates to a method for continuously coproducing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as a raw material, which comprises the following steps:
(1) Adding cracking carbon five from the lower part of the continuous reactor, adding maleic anhydride particles from the top of the continuous reactor, enabling the cracking carbon five to move upwards, enabling the maleic anhydride particles to move downwards, enabling cyclopentadiene in the cracking carbon five to react with the maleic anhydride particles, settling generated solid nadic anhydride to the bottom of the continuous reactor, and performing solid-liquid separation to obtain solid nadic anhydride; the incompletely reacted cracked carbon five liquid phase flows out from an overflow port at the upper part of the continuous reactor; the incompletely reacted cracked carbon five liquid phase contains isoprene, trans-1,3-pentadiene;
(2) Pumping the incompletely reacted cracked carbon five liquid phase flowing out of the overflow port in the step (1) and the maleic anhydride in a molten state into a microchannel reactor for reaction, and distilling the reacted liquid under reduced pressure to obtain the methyl tetrahydrophthalic anhydride.
Wherein:
in the step (1), the content of isoprene in the cracking carbon five is 10 to 25wt.%, the content of cyclopentadiene is 5 to 25wt.%, and the content of trans-1,3-pentadiene is 5 to 20wt.%; the main components of the cracking carbon five are shown in the table 1.
Preferably, in step (1), the cracked carbon five has an isoprene content of 18wt.%, a cyclopentadiene content of 18wt.%, and a trans-1,3-pentadiene content of 9wt.%.
TABLE 1 main components and contents thereof in cracking C5
In the step (1), the molar ratio of the maleic anhydride particles to cyclopentadiene in the cracking carbon five is 0.95-1.02, and the particle size of the maleic anhydride particles is 1-10mm.
In the step (1), the reaction temperature is between-10 ℃ and-1 ℃; the retention time is 30 to 90min.
In the step (1), the content of cyclopentadiene in the liquid phase of the incompletely reacted cracked carbon five is less than or equal to 1wt.%.
And (2) in the step (1), the generated solid-phase nadic anhydride is settled to the bottom of the continuous reactor, solid-liquid separation is carried out, and the obtained liquid is returned to the continuous reactor for recycling.
The molar ratio of the total molar amount of isoprene and trans-1,3-pentadiene in the cracking carbon five in the step (1) to the molar amount of maleic anhydride in the step (2) is 0.84 to 0.90.
In the step (2), the reaction temperature is 70-85 ℃, and the cracked carbon penta-liquid phase which is not completely reacted in the step (1) and maleic anhydride stay in the microchannel reactor for 4-7 min.
In the step (2), the maleic anhydride is heated to 65-90 ℃ to be in a molten state, and then is pumped into a microchannel reactor to react with the cracked carbon five liquid phase which is not completely reacted in the step (1).
In the step (2), the inner diameter of the microchannel reactor is 150 to 300 mu m; in the step (2), the pressure during reduced pressure distillation is 0.3 to 0.8MPa, and the reduced pressure distillation time is 30 to 40min.
The chemical reactions involved in the present invention are as follows:
(1) Reaction of cyclopentadiene with maleic anhydride to yield nadic anhydride:
(2) Isoprene reacts with maleic anhydride to produce 4-methyltetrahydrophthalic anhydride:
(3) Trans-1,3-pentadiene reacted with maleic anhydride to produce 3-methyltetrahydrophthalic anhydride:
the invention has the following beneficial effects:
(1) In a continuous reactor, maleic anhydride particles are added from the top of the continuous reactor, cracking carbon five is added from the lower part of the continuous reactor, the maleic anhydride particles move downwards, the cracking carbon five moves upwards, cyclopentadiene in the cracking carbon five reacts with the maleic anhydride particles under the condition of-10 ℃ to-1 ℃, generated solid nadic anhydride is settled to the bottom of the continuous reactor, and solid-liquid separation is carried out to obtain a solid-phase nadic anhydride crude product; the incompletely reacted cracked carbon five liquid phase flows out from an overflow port at the upper part of the continuous reactor.
The incompletely reacted cracked carbon five liquid phase contains isoprene and trans-1,3-pentadiene, which is because isoprene and trans-1,3-pentadiene do not react with maleic anhydride under the condition of-10 ℃ to-1 ℃.
And reacting the incompletely reacted cracked carbon penta liquid phase with maleic anhydride at 70-85 ℃ in a microchannel reactor, wherein isoprene reacts with the maleic anhydride to generate 4-methyltetrahydrophthalic anhydride, trans-1,3-pentadiene reacts with the maleic anhydride to generate 3-methyltetrahydrophthalic anhydride, and carrying out reduced pressure distillation to obtain the methyltetrahydrophthalic anhydride product.
The invention changes the traditional reaction mode for preparing solid nadic anhydride, and the essence of the reaction mode is that the two raw materials react in opposite movement. The continuous reaction is realized by the reaction mode that the maleic anhydride particles move downwards under the influence of gravity and the cracking carbon moves upwards, which is a great progress in the field.
The method directly utilizes different initiation temperatures of different components in industrial cracking carbon five, synthesizes nadic anhydride, 3-methyl tetrahydrophthalic anhydride and 4-methyl tetrahydrophthalic anhydride by adjusting the temperature, does not need to separate the cracking carbon five, reduces the consumption and reduces the production cost.
(2) The invention adopts continuous production, has long operation period and stable product quality.
(3) The method does not use a solvent during the synthesis of the nadic anhydride, does not introduce impurities, omits the step of subsequent solvent treatment, and provides a raw material for the co-production of the methyl tetrahydrophthalic anhydride while obtaining the nadic anhydride product.
(4) The invention uses the microchannel reactor for continuous production during the synthesis of the methyl tetrahydrophthalic anhydride, does not introduce additional polymerization inhibitor, improves the production efficiency, avoids the loss of the reactor caused by continuous temperature rise and temperature reduction, and omits the step of removing the polymerization inhibitor. And the microchannel reactor has the characteristics of high mass transfer and heat transfer efficiency, can efficiently control the reaction temperature, avoid temperature runaway, improve the safety of the production process and reduce the cost.
Drawings
FIG. 1 is a process flow diagram of the present invention;
wherein: 1. a continuous reactor; 2. crude nadic anhydride; 3. an overflow port; 4. a microchannel reactor; 5. and a temporary storage tank for the decyclization carbon five.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Adding 20g of cracking carbon five raw materials (the content of cyclopentadiene is 18wt.%, the content of isoprene is 18wt.%, the content of trans-1,3-pentadiene is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 5.240g of maleic anhydride particles (the particle size is 1-5 mm) from the top of the continuous reactor for reaction at-5 ℃, staying and reacting reactants in the continuous reactor for 60min, after the reaction is finished, allowing the incompletely reacted cracking carbon five liquid phase to flow out from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, performing solid-liquid separation on the solid-liquid mixture to obtain a solid-phase nadic anhydride crude product, drying the nadic anhydride crude product to obtain a solid-phase nadic anhydride product, wherein the yield is 98%, the purity is 97% by gas chromatography detection, and the melting point is above 140 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping incompletely reacted cracked carbon pentaliquid phase (cyclopentadiene content is less than 1 wt.%) flowing out of an overflow port in the step (1) and 8.945g of maleic anhydride in a molten state (75 ℃) into a microchannel reactor (with the inner diameter of 200 mu m) by using a metering pump and a high-temperature metering pump respectively, reacting for 4min at 70 ℃, collecting liquid at an outlet, and carrying out reduced pressure distillation on the collected liquid for 40min at 0.6MPa to obtain a methyl tetrahydrophthalic anhydride product, wherein the yield is 96%, and the purity is 97% by gas chromatography detection.
Example 2
(1) Adding 40g of cracking carbon five raw material (the cyclopentadiene content is 18wt.%, the isoprene content is 18wt.%, and the trans-1,3-pentadiene content is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 10.480g of maleic anhydride particles (the particle size is 5-10mm) from the top of the continuous reactor at the temperature of-10 ℃ for reaction, staying and reacting reactants in the continuous reactor for 80min, after the reaction is finished, allowing an incompletely reacted cracking carbon five liquid phase to flow out from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, performing solid-liquid separation on the solid-liquid mixture to obtain a solid-phase crude product of nano-dick anhydride, drying the crude product of nano-dick anhydride to obtain a solid-phase product, wherein the yield is 97%, and the purity is 98% by gas chromatography detection, and the melting point is higher than 138 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping incompletely reacted cracked carbon pentaliquid phase (cyclopentadiene content is less than 1 wt.%) flowing out of an overflow port in the step (1) and 17.890g of maleic anhydride in a molten state (85 ℃) into a microchannel reactor (with the inner diameter of 150 microns) by using a metering pump and a high-temperature metering pump respectively, reacting for 6min at 80 ℃, collecting liquid at an outlet, carrying out reduced pressure distillation on the collected liquid for 35min at 0.7MPa to obtain a methyl tetrahydrophthalic anhydride product, wherein the yield is 99%, and the purity is 98% by gas chromatography detection.
Example 3
(1) Adding 20g of cracking carbon five raw material (the cyclopentadiene content is 18wt.%, the isoprene content is 18wt.%, and the trans-1,3-pentadiene content is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 5.090g of maleic anhydride particles (the particle size is 5-10mm) from the top of the continuous reactor at the temperature of-1 ℃ for reaction, staying and reacting reactants in the continuous reactor for 50min, after the reaction is finished, allowing an incompletely reacted cracking carbon five liquid phase to flow out from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, performing solid-liquid separation on the solid-liquid mixture to obtain a solid-phase crude product of nano-dick anhydride, drying the crude product of nano-dick anhydride to obtain a solid-phase product, wherein the yield is 95%, and the purity is 96% by gas chromatography detection, and the melting point is above 135 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping the incompletely reacted cracked carbon penta-liquid phase (the content of cyclopentadiene is less than 1 wt.%) flowing out of the overflow port in the step (1) and 8.689g of maleic anhydride in a molten state (at 65 ℃) into a micro-channel reactor (with the inner diameter of 200 microns) by using a metering pump and a high-temperature metering pump respectively, reacting for 7min at 70 ℃, collecting liquid at an outlet, and carrying out reduced pressure distillation on the collected liquid for 30min at 0.6MPa to obtain a methyl tetrahydrophthalic anhydride product, wherein the yield is 98%, and the purity is 96% by gas chromatography detection.
Example 4
(1) Adding 20g of cracking carbon five raw material (the cyclopentadiene content is 18wt.%, the isoprene content is 18wt.%, and the trans-1,3-pentadiene content is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 5.345g of maleic anhydride particles (the particle size is 5-10mm) from the top of the continuous reactor under the condition of-3 ℃ for reaction, staying and reacting reactants in the continuous reactor for 30min, after the reaction is finished, allowing an incompletely reacted cracking carbon five liquid phase to flow out from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid-phase crude product of nano-dick anhydride, drying the crude product of nano-dick anhydride to obtain a solid-phase product, wherein the yield is 96%, and the purity is 96% by gas chromatography detection, and the melting point is above 135 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping incompletely reacted cracked carbon pentaliquid phase (cyclopentadiene content is less than 1 wt.%) flowing out of an overflow port in the step (1) and 9.124g of maleic anhydride in a molten state (at 90 ℃) into a microchannel reactor (with the inner diameter of 150 microns) by using a metering pump and a high-temperature metering pump respectively, reacting for 4min at 85 ℃, collecting liquid at an outlet, and carrying out reduced pressure distillation on the collected liquid for 40min at 0.5MPa to obtain a methyl tetrahydrophthalic anhydride product, wherein the yield is 94%, and the purity is 97% by gas chromatography detection.
Example 5
(1) Adding 20g of cracking carbon five raw materials (the content of cyclopentadiene is 18wt.%, the content of isoprene is 18wt.%, the content of trans-1,3-pentadiene is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 5.240g of maleic anhydride particles (the particle size is 1-5 mm) from the top of the continuous reactor at the temperature of-10 ℃ for reaction, staying and reacting reactants in the continuous reactor for 40min, after the reaction is finished, allowing the incompletely reacted cracking carbon five liquid phase to flow out from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, performing solid-liquid separation on the solid-liquid mixture to obtain a solid-phase nadic anhydride crude product, drying the nadic anhydride crude product to obtain a solid-phase nadic anhydride product, wherein the yield is 97%, the purity is 98% by gas chromatography detection, and the melting point is more than 137 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping incompletely reacted cracked carbon pentaliquid phase (cyclopentadiene content is less than 1 wt.%) flowing out of the overflow port in the step (1) and 8.945g of maleic anhydride in a molten state (75 ℃) into a microchannel reactor (with the inner diameter of 300 mu m) by using a metering pump and a high-temperature metering pump respectively, reacting for 5min at 80 ℃, collecting liquid at an outlet, and carrying out reduced pressure distillation on the collected liquid for 40min at 0.8MPa to obtain a methyl tetrahydrophthalic anhydride product, wherein the yield is 99%, and the purity is 98% by gas chromatography detection.
Example 6
(1) Adding 20g of cracking carbon five raw material (the cyclopentadiene content is 18wt.%, the isoprene content is 18wt.%, and the trans-1,3-pentadiene content is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 5.451g of maleic anhydride particles (the particle size is 1-5 mm) from the top of the continuous reactor for reaction at-8 ℃, remaining the reactant in the continuous reactor for reaction for 70min, after the reaction is finished, flowing out the cracking carbon five liquid phase which is not completely reacted from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, performing solid-liquid separation on the solid-liquid mixture to obtain a solid-phase nadic anhydride crude product, drying the nadic anhydride crude product to obtain a solid-phase nadic anhydride product, wherein the yield is 97%, and the purity is 98% by gas chromatography detection, and the melting point is above 137 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping incompletely reacted cracked carbon five liquid phase (cyclopentadiene content is less than 1 wt.%) flowing out of an overflow port in the step (1) and 9.310g of molten maleic anhydride (85 ℃) into a microchannel reactor (with the inner diameter of 200 microns) by using a metering pump and a high-temperature metering pump respectively, reacting for 5min at 80 ℃, collecting liquid at an outlet, carrying out reduced pressure distillation on the collected liquid for 40min at 0.3MPa to obtain a methyl tetrahydrophthalic anhydride product, wherein the yield is 99%, and the purity is 97% by gas chromatography detection.
Example 7
(1) Adding 10g of cracking carbon five raw material (the cyclopentadiene content is 18wt.%, the isoprene content is 18wt.%, and the trans-1,3-pentadiene content is 9 wt.%) from the lower part of a continuous reactor, replacing air in the continuous reactor with nitrogen, adding 2.620g of maleic anhydride particles (the particle size is 5-10mm) from the top of the continuous reactor at the temperature of-5 ℃ for reaction, allowing reactants to stay in the continuous reactor for reaction for 90min, after the reaction is finished, allowing an incompletely reacted cracking carbon five liquid phase to flow out from an overflow port at the upper part of the continuous reactor, collecting a solid-liquid mixture from the bottom of the continuous reactor, performing solid-liquid separation on the solid-liquid mixture to obtain a solid-phase crude product of nano-dick anhydride, drying the crude product of nano-dick anhydride to obtain a solid-phase product, wherein the yield is 98%, the purity is 99% by gas chromatography detection, and the melting point is more than 137 ℃; liquid obtained by solid-liquid separation is returned to the continuous reactor for recycling.
(2) Pumping incompletely reacted cracked carbon five liquid phase (cyclopentadiene content is less than 1 wt.%) flowing out of an overflow port in the step (1) and 4.472g of molten maleic anhydride (75 ℃) into a microchannel reactor (with the inner diameter of 150 microns) by using a metering pump and a high-temperature metering pump respectively, reacting for 5min at 75 ℃, collecting liquid at an outlet, carrying out reduced pressure distillation on the collected liquid for 40min at 0.6MPa to obtain a methyltetrahydrophthalic anhydride product, wherein the yield is 99%, and the purity is 98% by gas chromatography detection.
As shown in fig. 1, adding cracking carbon five raw material from the lower part of a continuous reactor 1, adding maleic anhydride particles, namely maleic anhydride particles, from the top of the continuous reactor 1, enabling the cracking carbon five raw material to move upwards and the maleic anhydride particles to move downwards, reacting cyclopentadiene in the cracking carbon five raw material with the maleic anhydride at-10 to-1 ℃, depositing the generated solid-phase nadic anhydride to the bottom of the continuous reactor 1, performing solid-liquid separation to obtain a solid-phase nadic anhydride crude product 2, and further drying the solid-phase nadic anhydride crude product 2 to obtain a solid-phase nadic anhydride product. The liquid obtained by solid-liquid separation, namely the recovered cracked carbon five, is returned to the continuous reactor 1 for recycling.
The liquid phase of the incompletely reacted cracked carbon five in the continuous reactor 1, namely the decyclized carbon five, flows out of an overflow port 3 at the upper part of the continuous reactor 1, firstly enters a decyclized carbon five temporary storage tank 5, and then enters a microchannel reactor 4 from the decyclized carbon five temporary storage tank 5; the incompletely reacted cracked carbon five liquid phase contains isoprene, trans-1,3-pentadiene;
pumping the incompletely reacted cracked carbon penta liquid phase in the temporary storage tank 5 for the decyclization carbon penta and the maleic anhydride in a molten state into the microchannel reactor 4, and reacting at the temperature of 70-85 ℃. Isoprene in the incompletely reacted cracked C-V liquid reacts with maleic anhydride to generate 4-methyltetrahydrophthalic anhydride, trans-1,3-pentadiene reacts with maleic anhydride to generate 3-methyltetrahydrophthalic anhydride, so that a crude product of the methyltetrahydrophthalic anhydride is obtained, and the crude product of the methyltetrahydrophthalic anhydride is subjected to reduced pressure distillation to obtain a methyltetrahydrophthalic anhydride product.
Claims (10)
1. A method for continuously coproducing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracked carbon five as a raw material is characterized by comprising the following steps:
(1) Adding cracking carbon five from the lower part of the continuous reactor, adding maleic anhydride particles from the top of the continuous reactor, enabling the cracking carbon five to move upwards, enabling the maleic anhydride particles to move downwards, enabling cyclopentadiene in the cracking carbon five to react with the maleic anhydride particles, settling generated solid nadic anhydride to the bottom of the continuous reactor, and performing solid-liquid separation to obtain solid nadic anhydride; the incompletely reacted cracked carbon five liquid phase flows out from an overflow port at the upper part of the continuous reactor; the incompletely reacted cracked carbon five liquid phase contains isoprene, trans-1,3-pentadiene;
(2) Pumping the incompletely reacted cracked carbon penta liquid phase flowing out of the overflow port in the step (1) and the maleic anhydride in a molten state into a micro-channel reactor for reaction, and distilling the reacted liquid under reduced pressure to obtain the methyl tetrahydrophthalic anhydride.
2. The method for continuously coproducing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked C5 as claimed in claim 1, wherein: in step (1), the cracked carbon five has an isoprene content of 18wt.%, a cyclopentadiene content of 18wt.%, and a trans-1,3-pentadiene content of 9wt.%.
3. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: in the step (1), the molar ratio of the maleic anhydride particles to cyclopentadiene in the cracking carbon five is 0.95-1.02, and the particle size of the maleic anhydride particles is 1-10mm.
4. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: in the step (1), the reaction temperature is between-10 ℃ and-1 ℃; the retention time is 30 to 90min.
5. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: in the step (1), the content of cyclopentadiene in the liquid phase of the incompletely reacted cracked carbon five is less than or equal to 1wt.%.
6. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: and (2) in the step (1), the generated solid-phase nadic anhydride is settled to the bottom of the continuous reactor, solid-liquid separation is carried out, and the obtained liquid is returned to the continuous reactor for recycling.
7. The method for continuously coproducing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked C5 as claimed in claim 1, wherein: the molar ratio of the total molar amount of isoprene and trans-1,3-pentadiene in the cracking carbon five in the step (1) to the molar amount of maleic anhydride in the step (2) is 0.84 to 0.90.
8. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: in the step (2), the reaction temperature is 70-85 ℃, and the cracked carbon penta-liquid phase which is not completely reacted in the step (1) and maleic anhydride stay in the microchannel reactor for 4-7 min.
9. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: in the step (2), the maleic anhydride is heated to 65-90 ℃ to be in a molten state, and then is pumped into a microchannel reactor to react with the cracked carbon five liquid phase which is not completely reacted in the step (1).
10. The method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride from cracked carbon five as claimed in claim 1, wherein: in the step (2), the inner diameter of the microchannel reactor is 150 to 300 mu m; in the step (2), the pressure during reduced pressure distillation is 0.3 to 0.8MPa, and the reduced pressure distillation time is 30 to 40min.
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