CN113583014A - Method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precise oxidation of durene - Google Patents
Method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precise oxidation of durene Download PDFInfo
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- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007791 liquid phase Substances 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 88
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- JGVFYLVFNVOUFN-UHFFFAOYSA-N [Co][Mn][Br][Zn] Chemical compound [Co][Mn][Br][Zn] JGVFYLVFNVOUFN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 229960000314 zinc acetate Drugs 0.000 claims description 7
- HNTLCLLUPYGURB-UHFFFAOYSA-N [2-(carboxymethyl)-4,5-dimethylphenyl]methanetricarboxylic acid Chemical compound C=1(C(C(=O)O)(C(=O)O)C(=O)O)C(CC(=O)O)=CC(C)=C(C)C1 HNTLCLLUPYGURB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000859 sublimation Methods 0.000 abstract description 4
- 230000008022 sublimation Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 11
- -1 Pyromellitic acid ester Chemical class 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- MUZPXEPSRLGFMT-UHFFFAOYSA-J tetrasodium;benzene-1,2,4,5-tetracarboxylate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C1=CC(C([O-])=O)=C(C([O-])=O)C=C1C([O-])=O MUZPXEPSRLGFMT-UHFFFAOYSA-J 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precise oxidation of durene in the technical field of organic chemical synthesis, which comprises the following steps of firstly, preparing and feeding durene, acetic acid and a cobalt-manganese-zinc-bromine catalyst according to the mass percentage of 5-20%: 79.97-94.99%: 0.01-0.05% of the mixture is completely mixed, and the mixed solution and the oxygen-enriched gas are continuously pumped into a micro-channel reactor for oxidation reaction; catalyzing and reacting to generate pyromellitic acid, and continuously discharging the generated pyromellitic acid-rich reaction liquid; then crystallizing and centrifuging, removing acetic acid, water and catalyst, and obtaining a filter cake, namely the refined pyromellitic acid; finally, dehydration is carried out to obtain the pyromellitic dianhydride. The method has the characteristics of high-speed mixing, high-efficiency heat transfer, short reactant retention time, high conversion rate, convenience in operation and control, low energy consumption of oxidation reaction, high safety coefficient, high purity of reaction products and no amplification effect, and a recrystallization or sublimation purification process is omitted.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a method for synthesizing pyromellitic dianhydride by liquid-phase oxidation of durene.
Background
Durene, also known as durene, is an important organic chemical raw material. The pyromellitic acid is mainly used for producing pyromellitic acid, and then the pyromellitic acid dianhydride is obtained by dehydration. Pyromellitic dianhydride is an important raw material for producing polyimide polymer, and polyimide is a novel synthetic material with high temperature resistance, low temperature resistance, radiation resistance and impact pressure resistance, excellent electrical property and mechanical property, and has important application which cannot be replaced by other engineering plastics in aerospace and electromechanical industries. With the continuous expansion of the market consumption of polyimide, durene is used as a main raw material for synthesizing the polyimide, and the demand is increased day by day.
The production line of pyromellitic dianhydride is divided into two types, one type is that the pyromellitic dianhydride is heated and melted, mixed with hot air after being gasified, and enters a fixed bed tubular reactor filled with a V-Ti-O catalyst and with the reaction temperature of 430-445 ℃ to generate pyromellitic anhydride and byproducts, and comprises a gasification section, an oxidation section, a trapping section, a hydrolysis section, a dehydration or sublimation refining section, a concentration section, a dehydration drying section and a recrystallization or sublimation section to generate pyromellitic acid or pyromellitic dianhydride; the other is liquid-phase oxidation of durene to synthesize reaction liquid rich in durene tetracarboxylic acid, which is then distilled, crystallized, centrifugally separated, dewatered to anhydride, recrystallized or sublimated to obtain the durene tetracarboxylic dianhydride.
Pyromellitic acid and its derivatives have industrially important applications. Pyromellitic acid is used as the main synthetic monomer of polyimide which is a high-temperature resistant insulating material, is widely applied to the fields of aerospace, aviation, electromechanics, electronics and the like, and is also an important curing agent for epoxy resin and polyester resin and an auxiliary agent for powder coating. The ortho carboxyl activity of sodium pyromellitate can generate chelate with polyvalent metal ion to be used as assistant of detergent. Pyromellitic acid ester is a good low-fluidity plasticizer and is also a PVC heat stabilizer. Phthalocyanine made from pyromellitic acid derivatives can be used as pigment, oxidation catalyst, and high-performance lubricant.
The microchannel reactor is essentially a continuous flow pipeline reactor, the microchannel is manufactured by using a precision machining process, and because the microchannel has a small size, compared with a conventional tubular reactor, the microchannel reactor has very large specific surface area and volume ratio, the microchannel reactor has extremely high mixing efficiency, extremely high heat transfer capacity and extremely narrow residence time distribution. Since the micro-reaction technology started to rise in the middle of the 90 s of the 20 th century, the micro-reaction technology is rapidly developed due to unique characteristics and advantages and becomes a common research hotspot in scientific research institutions and business industries; not only obtains a plurality of remarkable scientific research achievements, but also obtains more and more applications in the synthesis of medicines, pesticides, special materials, fine chemical products and intermediates.
Chinese patent CN111960939A discloses a method for producing pyromellitic acid, which comprises mixing and vaporizing durene serving as a raw material and air, and introducing the mixture into a microchannel reactor coated with a catalyst coating for reaction; cooling, crystallizing and centrifuging the reacted gas, distilling the centrifuged mother liquor at normal pressure, and adding the centrifuged solid and the distilled residual liquid into a hydrolysis kettle for hydrolysis; and finally, filtering the hydrolysate, and carrying out sectional cooling crystallization, centrifugation and vacuum drying on the filtrate to obtain the target product pyromellitic acid.
The existing gas phase or liquid phase oxidation process has the following defects:
1) the reaction temperature is higher, and the reaction energy consumption is high;
2) the reaction conversion rate is not high, and a plurality of byproducts are generated;
3) the process route is long, and the product is difficult to separate and purify.
Disclosure of Invention
The invention aims to provide a method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precise oxidation of durene, which has high conversion rate and easy purification of products.
The purpose of the invention is realized as follows: a method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precise oxidation of durene sequentially comprises the following steps:
(1) material preparation and feeding: durene, acetic acid and a cobalt-manganese-zinc-bromine catalyst are added according to the mass percentage of 5-20%: 79.97-94.99%: 0.01-0.05% of the mixture is completely mixed, and the mixed solution and the oxygen-enriched gas are continuously pumped into a micro-channel reactor for oxidation reaction;
(2) precision oxidation: keeping the oxidation temperature in the microchannel reactor at 180-260 ℃, keeping the pressure in the reactor at 1.2-1.8MPa, carrying out catalytic reaction on durene and oxygen-rich gas to generate durene tetracarboxylic acid, and continuously discharging the generated durene tetracarboxylic acid-rich reaction liquid;
(3) and (3) crystallizing and centrifuging: cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and a catalyst to obtain a filter cake, namely refined pyromellitic acid;
(4) dehydration to anhydride: the refined pyromellitic acid is sent into an anhydride forming kettle at 245 +/-2 ℃ and the vacuum degree of 0.095MPa for dehydration to obtain the pyromellitic dianhydride.
The further improvement is that the oxygen-enriched gas is a nitrogen-oxygen mixed gas with the oxygen volume content of 21-50%. The nitrogen plays a role in protection, and the oxygen plays a role in efficient oxidation. The inner diameter of the micro-channel reactor is 0.6-20 mu m. Preferably the inner diameter is 10 μm. On one hand, the micro-channel reactor has extremely large specific surface area due to the internal microstructure thereof, which can reach hundreds of times or even thousands of times of the specific surface area of the stirring kettle. On the other hand, the microchannel reactor has excellent heat transfer and mass transfer capacity, can realize instant uniform mixing and efficient heat transfer of materials, and can greatly accelerate the reaction process. The selection of the inner diameter of the microchannel not only can maintain the high-efficiency reaction of the microchannel reactor, but also can allow partial precipitates in the reaction to pass through, and is not easy to cause the blockage of the microchannel.
The further improvement of the invention is that the cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane. The preferred scheme is that the molar ratio of cobalt, manganese, zinc and bromine in the cobalt-manganese-zinc-bromine catalyst is 1:1:0.5: 0.5. The scheme is obtained by screening, and has a high-efficiency catalysis effect.
Compared with the prior art, the invention has the following beneficial effects: compared with the existing gas phase or liquid phase oxidation reaction, the method has the characteristics of high-speed mixing, high-efficiency heat transfer, short reactant retention time, high conversion rate, no need of recrystallization or sublimation purification process, convenience in operation and control, low energy consumption of the oxidation reaction, high safety coefficient, high purity of reaction products and no amplification effect.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed includes, but is not limited to, the scope of the examples.
Example 1:
continuously pumping mixed liquid of durene, acetic acid and cobalt-manganese-zinc bromide catalyst (mass ratio is 5: 94.99: 0.01) into a microchannel reactor, and continuously introducing air into a microchannel device while feeding the liquid, wherein the inner diameter of a microchannel of the microchannel reactor is 10 mu m.
The cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane, wherein the molar ratio of cobalt to manganese to zinc to bromine is 1:1:0.5: 0.5.
Keeping the temperature in the microchannel reactor at 180 ℃, the pressure in the reactor at 1.2MPa, carrying out catalytic reaction on durene and oxygen to generate pyromellitic acid, and continuously discharging the generated pyromellitic acid-rich reaction liquid, wherein the content of the pyromellitic acid in the reaction liquid is 98.5 percent.
Cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and catalyst to obtain a filter cake, namely the refined pyromellitic acid. Finally, the refined pyromellitic acid is sent into an anhydride forming kettle at 245 ℃ and the vacuum degree of 0.095MPa for dehydration to obtain pyromellitic dianhydride with the purity of 99.3 percent.
Example 2:
continuously pumping mixed liquid of durene, acetic acid and cobalt manganese zinc bromide catalyst (mass ratio is 17: 82.98: 0.02) into a microchannel reactor, continuously introducing oxygen-enriched gas into a microchannel device while feeding the liquid, wherein the oxygen content is 30%, and the inner diameter of a microchannel of the microchannel reactor is 10 mu m.
The cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane, wherein the molar ratio of cobalt to manganese to zinc to bromine is 1:1:0.5: 0.5.
Keeping the temperature in the microchannel reactor at 260 ℃, the pressure in the reactor at 1.8MPa, carrying out catalytic reaction on durene and oxygen to generate pyromellitic acid, and continuously discharging the generated pyromellitic acid-rich reaction liquid, wherein the content of the pyromellitic acid in the reaction liquid is 98.6 percent.
Cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and catalyst to obtain a filter cake, namely the refined pyromellitic acid. Finally, the mixture is sent into an anhydride forming kettle at 245 ℃ and dehydrated under the vacuum degree of 0.095MPa to obtain pyromellitic dianhydride with the purity of 99.4 percent.
Example 3:
continuously pumping mixed liquid of durene, acetic acid and cobalt manganese zinc bromide catalyst (mass ratio is 10: 89.95: 0.05) into a microchannel reactor, continuously introducing oxygen-enriched gas into a microchannel device while feeding the liquid, wherein the oxygen content is 50%, and the inner diameter of a microchannel of the microchannel reactor is 20 mu m.
The cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane, wherein the molar ratio of cobalt to manganese to zinc to bromine is 1:1:0.5: 0.5.
The temperature in the microchannel reactor is kept at 220 ℃, the pressure in the reactor is 1.4MPa, durene and oxygen react catalytically to generate pyromellitic acid, the generated reaction liquid rich in the pyromellitic acid is discharged continuously, and the content of the pyromellitic acid in the reaction liquid is 98.8 percent.
Cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and catalyst to obtain a filter cake, namely the refined pyromellitic acid. Finally, the mixture is sent into an anhydride forming kettle at 245 +/-2 ℃ and the vacuum degree of 0.095MPa for dehydration to obtain the pyromellitic dianhydride with the purity of 99.8 percent.
Example 4:
continuously pumping mixed liquid of durene, acetic acid and cobalt manganese zinc bromide catalyst (mass ratio is 20: 79.97: 0.05) into a microchannel reactor, and continuously introducing oxygen-enriched gas into a microchannel device while feeding the liquid, wherein the oxygen content is 45%.
The cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane, wherein the molar ratio of cobalt to manganese to zinc to bromine is 1:1:0.5: 0.5.
Keeping the temperature in the microchannel reactor at 240 ℃, the pressure in the reactor at 1.6MPa, carrying out catalytic reaction on durene and oxygen to generate pyromellitic acid, and continuously discharging the generated pyromellitic acid-rich reaction liquid, wherein the content of the pyromellitic acid in the reaction liquid is 98.7 percent.
Cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and catalyst to obtain a filter cake, namely the refined pyromellitic acid. Finally, the mixture is sent into an anhydride forming kettle at 245 +/-2 ℃ and the vacuum degree of 0.095MPa for dehydration to obtain the pyromellitic dianhydride with the purity of 99.6 percent.
Example 5:
continuously pumping mixed liquid of durene, acetic acid and cobalt manganese zinc bromide catalyst (mass ratio is 15: 84.95: 0.05) into a microchannel reactor, continuously introducing oxygen-enriched gas into a microchannel device while feeding the liquid, wherein the oxygen content is 40%, and the inner diameter of a microchannel of the microchannel reactor is 0.6 mu m.
The cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane, wherein the molar ratio of cobalt to manganese to zinc to bromine is 1:1:0.5: 0.5.
Keeping the temperature in the microchannel reactor at 200 ℃, the pressure in the reactor at 1.7MPa, carrying out catalytic reaction on durene and oxygen to generate pyromellitic acid, and continuously discharging the generated pyromellitic acid-rich reaction liquid, wherein the content of the pyromellitic acid in the reaction liquid is 98.4 percent.
Cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and catalyst to obtain a filter cake, namely the refined pyromellitic acid. Finally, the mixture is sent into an anhydride forming kettle at 245 ℃ and dehydrated under the vacuum degree of 0.095MPa to obtain the pyromellitic dianhydride with the purity of 99.2 percent.
Comparative example
On the basis of example 1, the following comparative examples 1 to 16 were obtained, with the other parameters being kept constant and with the contents of the components in the catalyst being varied only, the results being shown in the following table:
it can be seen that when the molar ratio of the cobalt, manganese, zinc and bromine is 1:1:0.5:0.5, the pyromellitic acid content in the reaction solution is the highest, and the final yield is also the highest.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (6)
1. A method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precise oxidation of durene is characterized by sequentially comprising the following steps:
(1) material preparation and feeding: durene, acetic acid and a cobalt-manganese-zinc-bromine catalyst are added according to the mass percentage of 5-20%: 79.97-94.99%: 0.01-0.05% of the mixture is completely mixed, and the mixed solution and the oxygen-enriched gas are continuously pumped into a micro-channel reactor for oxidation reaction;
(2) precision oxidation: keeping the oxidation temperature in the microchannel reactor at 180-260 ℃, keeping the pressure in the reactor at 1.2-1.8MPa, carrying out catalytic reaction on durene and oxygen-rich gas to generate durene tetracarboxylic acid, and continuously discharging the generated durene tetracarboxylic acid-rich reaction liquid;
(3) and (3) crystallizing and centrifuging: cooling the pyromellitic acid reaction liquid to 25 ℃ for crystallization, separating in a centrifuge, removing acetic acid, water and a catalyst to obtain a filter cake, namely refined pyromellitic acid;
(4) dehydration to anhydride: the refined pyromellitic acid is sent into an anhydride forming kettle at 245 +/-2 ℃ and the vacuum degree of 0.095MPa for dehydration to obtain the pyromellitic dianhydride.
2. The method for synthesizing the pyromellitic dianhydride by the liquid-phase continuous oxygen-rich precision oxidation of the durene according to claim 1, is characterized in that: the oxygen-enriched gas is a nitrogen-oxygen mixed gas with the oxygen volume content of 21-50%.
3. The method for synthesizing the pyromellitic dianhydride by the liquid-phase continuous oxygen-rich precision oxidation of the durene according to claim 1, is characterized in that: the inner diameter of the micro-channel reactor is 0.6-20 mu m.
4. The method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-rich precision oxidation of durene according to claim 3, is characterized in that: the inner diameter of the micro-channel reactor is 10 mu m.
5. The method for synthesizing the pyromellitic dianhydride by the liquid-phase continuous oxygen-rich precision oxidation of the durene according to claim 1, is characterized in that: the cobalt-manganese-zinc-bromine catalyst is a mixture of cobalt acetate, manganese acetate, zinc acetate and tetrabromoethane.
6. The method for synthesizing pyromellitic dianhydride by liquid-phase continuous oxygen-enriched precision oxidation of durene according to any one of claims 1 to 5, characterized in that: the molar ratio of cobalt, manganese, zinc and bromine in the cobalt-manganese-zinc-bromine catalyst is 1:1:0.5: 0.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114369099A (en) * | 2021-12-21 | 2022-04-19 | 中海油天津化工研究设计院有限公司 | Method for preparing pyromellitic dianhydride by liquid-phase oxidation |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611482A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid oxidation residue recovery and utilization method |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| RU2004124881A (en) * | 2004-08-16 | 2006-01-27 | Общество с ограниченной ответственностью "Научно-исследовательский и производственный центр""ВНИПИМ-ТОС" (RU) | METHOD FOR PRODUCING AND CLEANING PYROMELLITE DIANHYDRIDE |
| CN1844187A (en) * | 2006-03-23 | 2006-10-11 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| CN101014561A (en) * | 2003-05-02 | 2007-08-08 | 万罗赛斯公司 | Process for converting a hydrocarbon to an oxygenate or a nitrile |
| CN102059141A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic carboxylic acid and application thereof |
| CN103265416A (en) * | 2013-05-23 | 2013-08-28 | 南京大学 | Method for preparing benzaldehyde from methylbenzene with high selectivity |
| CN107175128A (en) * | 2016-03-11 | 2017-09-19 | 中国石油化工股份有限公司 | Liquid phase oxidation prepares the catalyst of aromatic multi-carboxy acid |
| CN107282103A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic multi-carboxy acid |
| CN107866257A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is prepared for durol |
| CN108794321A (en) * | 2018-07-16 | 2018-11-13 | 山东冠森高分子材料科技股份有限公司 | The method that aromatic carboxylic-acid compound is synthesized in continuous flow micro passage reaction |
| CN110746435A (en) * | 2019-10-31 | 2020-02-04 | 曹正国 | Method for producing pyromellitic dianhydride by low-temperature liquid-phase continuous oxidation of durene |
| CN111960939A (en) * | 2020-08-18 | 2020-11-20 | 连云港鹏辰特种新材料有限公司 | Preparation method for preparing pyromellitic acid based on catalytic oxidation-hydrolysis-fractional crystallization |
-
2021
- 2021-08-17 CN CN202110941640.2A patent/CN113583014A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014561A (en) * | 2003-05-02 | 2007-08-08 | 万罗赛斯公司 | Process for converting a hydrocarbon to an oxygenate or a nitrile |
| CN1611482A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid oxidation residue recovery and utilization method |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| RU2004124881A (en) * | 2004-08-16 | 2006-01-27 | Общество с ограниченной ответственностью "Научно-исследовательский и производственный центр""ВНИПИМ-ТОС" (RU) | METHOD FOR PRODUCING AND CLEANING PYROMELLITE DIANHYDRIDE |
| CN1844187A (en) * | 2006-03-23 | 2006-10-11 | 华东理工大学华昌聚合物有限公司 | Process for producing terephthalic unsaturated polyester resin by using terephthalic acid rinsing residue |
| CN102059141A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic carboxylic acid and application thereof |
| CN103265416A (en) * | 2013-05-23 | 2013-08-28 | 南京大学 | Method for preparing benzaldehyde from methylbenzene with high selectivity |
| CN107175128A (en) * | 2016-03-11 | 2017-09-19 | 中国石油化工股份有限公司 | Liquid phase oxidation prepares the catalyst of aromatic multi-carboxy acid |
| CN107282103A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic multi-carboxy acid |
| CN107866257A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is prepared for durol |
| CN108794321A (en) * | 2018-07-16 | 2018-11-13 | 山东冠森高分子材料科技股份有限公司 | The method that aromatic carboxylic-acid compound is synthesized in continuous flow micro passage reaction |
| CN110746435A (en) * | 2019-10-31 | 2020-02-04 | 曹正国 | Method for producing pyromellitic dianhydride by low-temperature liquid-phase continuous oxidation of durene |
| CN111960939A (en) * | 2020-08-18 | 2020-11-20 | 连云港鹏辰特种新材料有限公司 | Preparation method for preparing pyromellitic acid based on catalytic oxidation-hydrolysis-fractional crystallization |
Non-Patent Citations (1)
| Title |
|---|
| 陈韶辉等: "均苯四甲酸二酐的合成工艺研究进展" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114369099A (en) * | 2021-12-21 | 2022-04-19 | 中海油天津化工研究设计院有限公司 | Method for preparing pyromellitic dianhydride by liquid-phase oxidation |
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