CN117946049A - Method for producing methyltetrahydrophthalic anhydride - Google Patents
Method for producing methyltetrahydrophthalic anhydride Download PDFInfo
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- CN117946049A CN117946049A CN202410346715.6A CN202410346715A CN117946049A CN 117946049 A CN117946049 A CN 117946049A CN 202410346715 A CN202410346715 A CN 202410346715A CN 117946049 A CN117946049 A CN 117946049A
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- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 42
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010457 zeolite Substances 0.000 claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 36
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- 238000010517 secondary reaction Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 238000003860 storage Methods 0.000 claims description 40
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 27
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 27
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 26
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 13
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 235000005074 zinc chloride Nutrition 0.000 claims description 12
- 239000011592 zinc chloride Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 150000001336 alkenes Chemical class 0.000 abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- -1 MTHPA Chemical compound 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002296 pyrolytic carbon Substances 0.000 description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 2
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 2
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SOOZEQGBHHIHEF-UHFFFAOYSA-N methyltetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21C SOOZEQGBHHIHEF-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of heterocyclic compounds, and particularly relates to a method for producing methyl tetrahydrophthalic anhydride. Sequentially carrying out alkali treatment, modification treatment, pre-coating seed crystal treatment and film growth treatment on the inner surface of a micro-channel of the micro-channel reactor to obtain the micro-channel reactor with the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite film on the inner surface of the micro-channel; introducing the carbon five and maleic anhydride into a microchannel reactor with a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane on the inner surface of the microchannel to perform a pre-reaction, then performing a secondary reaction, and separating to obtain the methyltetrahydrophthalic anhydride. According to the invention, the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane is prepared on the inner surface of a micro-channel of the micro-channel reactor, so that the effective contact area of the catalyst, the polymerization inhibitor and the raw materials is greatly increased, and the mass and heat transfer are further promoted; reduces the self-polymerization of olefin and avoids the problem of deterioration and coking of methyl tetrahydrophthalic anhydride caused by reduced pressure distillation.
Description
Technical Field
The invention belongs to the technical field of heterocyclic compounds, and particularly relates to a method for producing methyl tetrahydrophthalic anhydride.
Background
Methyl tetrahydrophthalic anhydride, namely MTHPA, is an organic anhydride epoxy resin curing agent with excellent performance, and the liquid methyl tetrahydrophthalic anhydride has the advantages of low viscosity, low toxicity, high stability, long shelf life and good compatibility, and has wide industrial application prospect. The methyl tetrahydrophthalic anhydride has nearly 20 isomers, mainly 3-methyl tetrahydrophthalic anhydride and 4-methyl tetrahydrophthalic anhydride, the market circulation finished products are a mixture of various isomers, the 3-methyl tetrahydrophthalic anhydride and the 4-methyl tetrahydrophthalic anhydride are solid at normal temperature, and the solid anhydride has more complicated operation and sublimation phenomenon due to the use temperature above the melting point of the curing agent, and has larger influence on the environment, so the development of the liquid anhydride curing agent becomes the main stream of research.
The Diels-Alder reaction, namely the D-A reaction, is a reaction of generating a six-membered ring compound by 1, 4-addition of a compound containing an active double bond or triple bond and a conjugated diene compound, and is one of the most widely used six-membered ring material synthesis methods at present.
At present, intermittent kettle reaction technology is mainly adopted in China to prepare crude methyl tetrahydrophthalic anhydride, namely maleic anhydride and carbon five are introduced into a reaction kettle, and a D-A reaction mechanism is utilized to prepare the methyl tetrahydrophthalic anhydride, but the D-A reaction is a strong exothermic reaction, the kettle reactor is easy to generate heat accumulation due to different reaction intensity caused by partial uneven contact, and self-polymerization can be generated under the high-temperature condition of olefin in the carbon five, so that the carbon five introduction rate is strictly controlled during the reaction, the partial violent reaction can be caused by too fast addition, the temperature is suddenly increased, irreversible self-polymerization can be generated on the olefin in the carbon five, and the production efficiency can be reduced due to too slow addition. To avoid the above problems, the use of a microchannel reactor is a simple and effective method.
The microchannel reactor is an integrated continuous reaction system which is manufactured by utilizing a micro-processing technology and consists of a reaction zone, a mixing zone, a heat exchange zone, a separation zone and other modules, wherein the reaction zone consists of microchannels with equivalent diameters of 10-1000 mu m, the gas-liquid mass transfer coefficient of the inner surface of each microchannel can reach the order of magnitude of 10 -3 m/s, the liquid-liquid mass transfer coefficient can reach the order of magnitude of 10 -6~10-4 m/s, and the heat and mass transfer performance is good, so that heat is not easy to accumulate, side reactions are avoided, and the safety coefficient is improved. However, the micro-channels have small size and complex structure, so that the reactor channels are extremely easy to block and difficult to clean; because the specific surface area of the micro-channel is large, the characteristic size is small, and the reaction performance is greatly influenced even if the micro-surface is corroded, the micro-channel material has higher corrosion resistance requirement, the manufacturing cost of the micro-channel reactor is certainly increased, and the industrial application is limited.
Chinese patent CN115572274a discloses a method for continuously co-producing nadic anhydride and methyltetrahydrophthalic anhydride by using pyrolytic carbon five as raw material, adding pyrolytic carbon five from the lower part of a continuous reactor, adding maleic anhydride particles from the top of the continuous reactor, reacting cyclopentadiene in the pyrolytic carbon five with maleic anhydride particles, and settling the generated solid-phase nadic anhydride to the bottom of the continuous reactor; the incomplete reacted cracked carbon five liquid phase flows out from an overflow port at the upper part of the continuous reactor; pumping the incompletely reacted cracking carbon five liquid phase and maleic anhydride in a molten state into a microchannel reactor for reaction to obtain methyl tetrahydrophthalic anhydride. In the patent, maleic anhydride has a solidifying point of 52.8 ℃ and is corrosive, and micro-channels are easy to corrode during long-term production, so that the reaction performance is affected.
Chinese patent CN114669256a discloses a process and apparatus for producing methyl tetrahydrophthalic anhydride, the process for producing methyl tetrahydrophthalic anhydride comprises the following steps: s1, preparing enough raw materials of piperylene, isoprene and maleic anhydride; s2, respectively placing the piperylene and the isoprene into corresponding metering tanks for storage, then calculating the corresponding proportion of the piperylene and the isoprene according to production requirements, opening the metering tanks filled with the piperylene and the isoprene, and proportionally conveying the metering tanks into corresponding charging barrels; the production equipment of the methyl tetrahydrophthalic anhydride comprises a synthesis kettle, a metering and feeding device, a driving transmission device, a scraping device, a stirring device and a heating control device. The patent relates to a batch kettle reaction process, which is easy to generate heat accumulation, leads to olefin self-polymerization, and causes raw material waste and complex subsequent impurity separation process.
Disclosure of Invention
The invention aims to provide a method for producing methyl tetrahydrophthalic anhydride, which utilizes the strong mass and heat transfer effect of a microchannel reactor, realizes the high-quality production of methyl tetrahydrophthalic anhydride under the action of a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane on the inner surface of the microchannel, and solves the problems that olefin in carbon five is easy to self-polymerize and the subsequent impurity separation process is complex due to kettle-type reaction heat accumulation and the inner surface of the microchannel is corroded when the microchannel reactor is used.
The method for producing methyl tetrahydrophthalic anhydride comprises the steps of sequentially carrying out alkali treatment, modification treatment, pre-coating seed crystal treatment and film growth treatment on the inner surface of a micro-channel reactor to obtain the micro-channel reactor with a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite film on the inner surface of the micro-channel; introducing the carbon five and maleic anhydride into a microchannel reactor with a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane on the inner surface of the microchannel to perform a pre-reaction, then performing a secondary reaction, and separating to obtain the methyltetrahydrophthalic anhydride.
The preparation method of the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane comprises the following steps:
(1) Uniformly mixing a diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution and a zinc chloride aqueous solution, regulating the pH, stirring, filtering, washing with water, concentrating and drying to obtain a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex; adding zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex into ethanol water solution, stirring, sequentially adding sodium metaaluminate and ethyl silicate, stirring, standing, crystallizing, centrifuging, washing with water, and adding ethanol to obtain seed suspension;
(2) Sequentially adding ethanol and ethyl silicate into the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution, stirring, and sequentially adding sodium metaaluminate and sodium sulfate, stirring to obtain a membrane synthetic solution;
(3) Sequentially introducing alkali liquor into a micro-channel of a micro-channel reactor for alkali treatment, introducing water for water washing treatment, introducing an ethanol solution of an amino silane coupling agent for modification treatment, introducing seed suspension for pre-coating seed crystal treatment, introducing film synthesis liquid for film growth treatment, introducing water for water washing treatment, and drying to obtain the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite film.
The mass concentration of the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution in the step (1) is 15-25 wt%, and the mass ratio of the Diethylhydroxylamine (DEHA) to the dodecatungstophosphoric acid (PTA) in the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution is 2-2.4:1.3 to 1.5, wherein the molar concentration of the zinc chloride aqueous solution is 0.01 to 0.09mol/L, and the mass ratio of the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution to the zinc chloride aqueous solution is 1:1.5 to 2.6; adjusting the pH to 4-4.5; the ratio of the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex to the ethanol aqueous solution to the sodium metaaluminate to the ethyl silicate (TEOS) is 3-8:35-40:0.1-0.2:8-12, wherein the zinc-diethyl hydroxylamine-dodecatungsten phosphate complex and sodium metaaluminate are calculated in g, and the ethanol aqueous solution and the ethyl silicate are calculated in mL; the volume ratio of ethanol and water in the ethanol water solution is 5-7:30-33, the crystallization temperature is 110-130 ℃, the crystallization time is 13-15h, and the concentration of the seed suspension is 0.5-2wt.%.
In the step (2), the proportion of the diethylhydroxylamine, the dodecatungstophosphoric acid and the deionized water in the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution is 2.0-2.5:1.0-1.5:70, wherein, the diethyl hydroxylamine and the dodecatungstophosphoric acid are calculated in g and the deionized water is calculated in mL; the proportion of the diethylhydroxylamine, the ethanol, the ethyl silicate, the sodium metaaluminate and the sodium sulfate in the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution is 2.0-2.5:8-10:5-7:0.1-0.2:0.2-0.3, wherein, the contents of diethyl hydroxylamine, sodium metaaluminate and sodium sulfate are calculated in g, and the contents of ethanol and ethyl silicate are calculated in mL.
The alkali liquor in the step (3) is sodium hydroxide solution, and the alkali treatment time is 1-2h; the volume ratio of the amino silane coupling agent to the ethanol in the ethanol solution of the amino silane coupling agent is 1:10-20, wherein the amino silane coupling agent is 3-aminopropyl trimethoxy silane (APTMS), the modification treatment temperature is 60-80 ℃, and the modification treatment time is 1-2h; the pre-coating seed crystal treatment temperature is 60-80 ℃, and the pre-coating seed crystal treatment time is 1-2h; the film growth treatment temperature is 95-100 ℃, and the film growth treatment time is 1-3h; the drying temperature is 30-50 ℃.
The composition of the carbon five comprises isoprene and trans-1, 3-pentadiene, the ratio of the total mole number of the isoprene and the trans-1, 3-pentadiene to the mole number of maleic anhydride in the carbon five is 1.01-1.05:1, and the flow rate ratio of the carbon five to the maleic anhydride is 2-2.5:1.
The pre-reaction temperature is 35-75 ℃, and the pre-reaction time is 48-106s.
The temperature of the secondary reaction is 35-75 ℃, and the time of the secondary reaction is 20-30min.
The separation temperature is 40-60 ℃.
The device for producing the methyl tetrahydrophthalic anhydride comprises a first carbon five storage tank, a second carbon five storage tank and a third carbon five storage tank, wherein the first carbon five storage tank, a first advection pump and a micro-channel reactor are sequentially connected, the second carbon five storage tank, the second advection pump and the micro-channel reactor are sequentially connected, the third carbon five storage tank, the third advection pump and the micro-channel reactor are sequentially connected, the micro-channel reactor, a high temperature heating pump and a MA melting tank are sequentially connected, the micro-channel reactor, a kettle type reactor, a vacuum pump and a separation tank are sequentially connected, a stainless steel cutting sleeve micro-adjusting valve is arranged between the micro-channel reactor and the kettle type reactor, the kettle type reactor is connected with the second cold and hot integrated circulation pump, and the separation tank is respectively connected with a carbon five receiving tank and a finished product tank.
The temperature of the carbon five in the first carbon five storage tank is 10-12 ℃, the temperature of the carbon five in the second carbon five storage tank is 20-22 ℃, and the temperature of the carbon five in the third carbon five storage tank is 30-32 ℃.
The flow rates of the first advection pump, the second advection pump and the third advection pump are all 0.01-30ml/min, and the pressures are all 0-20MPa.
The flow rate of the high-temperature heating pump is 0.1-100ml/min, and the pressure is 0-20MPa.
The microchannel reactor comprises 3 microchannel modules with 2 multiplied by 16 channels, the microchannel modules are made of stainless steel materials, the 3 microchannel modules are arranged in series, each microchannel module is provided with two sample inlets, and the outlet of the microchannel reactor is connected with the kettle type reactor.
The stainless steel shell of the microchannel reactor is provided with an inlet and an outlet of external circulation and is connected with a first cold and hot integrated circulating pump.
The microchannel reactor is a microchannel reactor with a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane on the inner surface of the microchannel.
The method for producing methyl tetrahydrophthalic anhydride comprises the following specific steps:
Adding 10-12 ℃ of carbon five in a first carbon five storage tank, 20-22 ℃ of carbon five in a second carbon five storage tank and 30-32 ℃ of carbon five in a third carbon five storage tank into 3 micro-channel modules of a micro-channel reactor respectively; maleic anhydride is added into an MA melting tank, heated and melted, and the maleic anhydride after the heating and melting is conveyed into a micro-channel reactor through a high-temperature heating pump; the method comprises the steps of pre-reacting carbon five and maleic anhydride in a micro-channel reactor with zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of the micro-channel, regulating the back pressure of a system to be 0.4-0.8MPa through a stainless steel cutting sleeve fine-tuning valve, enabling materials to enter a kettle-type reactor after the pre-reaction to carry out secondary reaction, enabling the materials to enter a separation tank to carry out separation after the secondary reaction is finished, recycling unreacted carbon five to a carbon five receiving tank, and enabling the product methyltetrahydrophthalic anhydride to enter a finished product tank.
The heating and melting temperature is 60-62 ℃, and the heating and melting time is 2.2-2.5h.
The temperatures of the pump head, the pump seat, the inlet and the outlet of the high-temperature heating pump are all set to be 60-62 ℃.
The effect of adding the carbon five with different temperatures in sections in the invention is to accelerate the reaction and prevent the olefin from self-polymerization.
The invention provides a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane on the inner surface of a micro-channel reactor, which has higher reaction selectivity and great advantage for D-A reaction. ZnCl 2 as Lewis acid catalyst can coordinate with p bond of olefin to provide activation center for reaction, speed up reaction and raise reaction selectivity. The N-O bond in diethylhydroxylamine can undergo an addition reaction with free radicals to prevent polymerization of olefins. The method is characterized in that the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid micro zeolite membrane is prepared by a seed crystal method by taking dodecatungstophosphoric acid with the same catalytic effect as a template agent, the reaction rate is accelerated by utilizing the synergistic catalytic action of dodecatungstophosphoric acid and zinc, and the self-polymerization of olefins is prevented by the addition of diethyl hydroxylamine and the steric effect, so that the efficient synthesis of methyltetrahydrophthalic anhydride by the D-A reaction in a microchannel is realized.
According to the invention, a complex is formed between the dodecatungstophosphoric acid and zinc, and the complex attracts diethyl hydroxylamine through intermolecular force to form a stable catalytic polymerization inhibition system, and compared with free diethyl hydroxylamine, the zeolite membrane is prepared to play a role, so that the stability of the diethyl hydroxylamine to free radical addition is ensured, and the effect of the diethyl hydroxylamine in preventing olefin self-polymerization is exerted, thereby realizing efficient synthesis of methyl tetrahydrophthalic anhydride through D-A reaction in a microchannel.
The invention creatively combines the micro-channel reactor with the kettle-type reactor, adopts the micro-channel reactor to carry out the pre-reaction before the kettle-type reactor, and solves the problem that the kettle-type reactor is easy to generate heat accumulation to cause self-polymerization of olefins in five carbon atoms under the high temperature condition. However, when the traditional microchannel reactor is used for the reaction, the reaction is unstable, and the problem of high-temperature self-polymerization of olefins in the carbon five is not solved, so that the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane is prepared on the inner surface of the microchannel, thereby realizing the high-quality production of methyl tetrahydrophthalic anhydride, and solving the problems that heat accumulation is easy to occur in the kettle reactor and the inner surface of the microchannel is corroded when the microchannel reactor is used.
The beneficial effects of the invention are as follows:
According to the invention, the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane is prepared on the inner surface of a micro-channel of the micro-channel reactor, so that the effective contact area of the catalyst, the polymerization inhibitor and the raw materials is greatly increased, and the mass and heat transfer are further promoted; the self-polymerization of olefin is reduced, the problem of deterioration and coking of methyl tetrahydrophthalic anhydride caused by reduced pressure distillation is avoided, the yield of the methyl tetrahydrophthalic anhydride reaches more than 99 percent, and the carbon five consumption is reduced; the reaction rate is improved, and the reaction time is reduced; the corrosion of the raw materials to the micro-channel is reduced by coating the inner surface of the micro-channel by the membrane.
Drawings
FIG. 1 is an SEM characterization of a zinc-diethylhydroxylamine-dodecatungstophosphoric acid zeolite membrane;
FIG. 2 is a schematic view of the structure of the device of the present invention;
In the figure: 1. a first carbon five reservoir; 2. a first advection pump; 3. a second carbon five reservoir; 4. a second parallel flow pump; 5. a third carbon five reservoir; 6. a third advection pump; 7. MA melting pot; 8. a high temperature heating pump; 9. a microchannel reactor; 10. a first cold and hot integrated circulating pump; 11. stainless steel cutting ferrule trim valve; 12. a tank reactor; 13. a second cold and hot integrated circulating pump; 14. a vacuum pump; 15. a separation tank; 16. a carbon five receiving tank; 17. and a finished product groove.
Detailed Description
The present invention is specifically described and illustrated below with reference to examples.
Example 1
The preparation method of the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane comprises the following steps:
(1) 61g of diethylhydroxylamine, 39g of dodecatungstophosphoric acid and deionized water to prepare 500g of 20wt.% diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution, 6.816gZnCl 2 and 1000g of water to prepare 0.05mol/L zinc chloride aqueous solution; uniformly mixing the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution and the zinc chloride aqueous solution, regulating the pH value to be 4.2 by hydrochloric acid, stirring for 2 hours to generate gel, filtering by a 400-mesh screen, washing by a small amount of water, concentrating and drying to obtain a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex;
5.4023g of zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex is added into 38mL of ethanol aqueous solution (obtained by mixing 32mL of deionized water and 6.0mL of ethanol) and stirred for 10min, 0.1324g of NaAlO 2 is added, mixed and stirred until clear, 10.3mL of ethyl silicate is added dropwise at room temperature and stirred until completely clear, the mixture is left to stand for 6h, after crystallization for 14h at 120 ℃ in a hydrothermal synthesis kettle, the mixture is centrifuged, water is washed to pH <8, and ethanol is added to prepare 1wt.% seed suspension.
(2) 2.2335G of diethylhydroxylamine and 1.4682g of dodecatungstophosphoric acid were mixed with 70mL of deionized water to obtain a diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution, 9mL of ethanol and 5.5mL of ethyl silicate were sequentially added to the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution and stirred for 4 hours, and 0.1215g of NaAlO 2 and 0.27g of Na 2SO4 were sequentially added and stirred for 1 hour at room temperature to obtain a clear film composition.
(3) Sequentially introducing NaOH solution into a microchannel of a microchannel reactor for alkali treatment for 1.5h, introducing water for water washing treatment, introducing ethanol solution of 3-aminopropyl trimethoxy silane (the volume ratio of 3-aminopropyl trimethoxy silane to ethanol is 1:15) for modification treatment at 60 ℃ for 2h, introducing 1wt.% seed suspension obtained in the step (1) at the flow rate of 1.55mL/h for pre-seeding treatment at 60 ℃ for 2h, introducing ethanol for cleaning and then drying for 1h, introducing the film synthesis liquid obtained in the step (2) at the flow rate of 1.55mL/h for film growth treatment at 98 ℃ for 2h, introducing water for water washing treatment, and drying at 40 ℃ for 12h to obtain the zinc-diethylhydroxylamine-dodecatungsten phosphate zeolite film, wherein the SEM characterization diagram of the zinc-diethylhydroxylamine-dodecatungsten phosphate zeolite film is shown in figure 1.
As shown in fig. 2, the apparatus used in the method for producing methyl tetrahydrophthalic anhydride comprises a first carbon five storage tank 1, a second carbon five storage tank 3 and a third carbon five storage tank 5, wherein the first carbon five storage tank 1 and the first advection pump 2 are sequentially connected with a micro-channel reactor 9, the second carbon five storage tank 3 and the second advection pump 4 are sequentially connected with the micro-channel reactor 9, the third carbon five storage tank 5 and the third advection pump 6 are sequentially connected with the micro-channel reactor 9, the micro-channel reactor 9 and the high temperature heating pump 8 are sequentially connected with a MA melt tank 7, the micro-channel reactor 9 is sequentially connected with a first cold and hot integrated circulating pump 10, the micro-channel reactor 9, a kettle type reactor 12 and a vacuum pump 14 are sequentially connected with a separation tank 15, a stainless steel cutting sleeve fine tuning valve 11 is arranged between the micro-channel reactor 9 and the kettle type reactor 12 is sequentially connected with a second cold and hot integrated circulating pump 13, and the separation tank 15 is respectively connected with a carbon five receiving tank 16 and a finished product tank 17.
The microchannel reactor 9 comprises 3 microchannel modules with 2×16 channels, the 3 microchannel modules are arranged in series, each microchannel module is provided with two sample inlets, and the outlet of the microchannel reactor 9 is connected with the kettle reactor 12.
The microchannel reactor 9 is a microchannel reactor with a zinc-diethylhydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of the microchannel.
The carbon five composition is shown in table 1.
Adding 10 ℃ of carbon five in a first carbon five storage tank 1, 20 ℃ of carbon five in a second carbon five storage tank 3 and 30 ℃ of carbon five in a third carbon five storage tank 5 into 3 micro-channel modules of a micro-channel reactor 9 respectively, wherein the total flow rate of a first advection pump 2, a second advection pump 4 and a third advection pump 6 is 17ml/min; maleic anhydride is added into an MA melting tank 7, heated and melted at 60 ℃ for 2.5 hours, and the maleic anhydride after being heated and melted is conveyed into a micro-channel reactor 9 through a high-temperature heating pump 8, wherein the flow rate of the high-temperature heating pump 8 is 7.3ml/min; maleic anhydride in a microchannel reactor 9 with a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of a microchannel sequentially passes through 3 microchannel modules to be pre-reacted with carbon five, the ratio of the total mole number of isoprene and trans-1, 3-pentadiene in the carbon five to the mole number of maleic anhydride is 1.01:1, the pre-reaction temperature is regulated to 55 ℃ by a first cold and hot integrated circulating pump 10, the pre-reaction time is 78s, the back pressure of the system is regulated to 0.4-0.8MPa by a stainless steel cutting sleeve micro-regulating valve 11, materials enter a kettle type reactor 12 to be subjected to secondary reaction at 55 ℃ for 30min after the pre-reaction is finished, the materials enter a separation tank 15 to be separated after the secondary reaction, the separation temperature is 40 ℃, the unreacted carbon five in a gas phase enters a carbon five receiving tank 16, and the liquid-phase product methyl tetrahydrophthalic anhydride enters a finished product tank 17.
The yield of the product methyl tetrahydrophthalic anhydride is 99.31 percent.
Example 2
The preparation method of the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane comprises the following steps:
(1) 45g of diethylhydroxylamine, 30g of dodecatungstophosphoric acid and deionized water to prepare 500g of 15wt.% diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution, 1.022gZnCl 2 and 750g of water to prepare 0.01mol/L zinc chloride aqueous solution; uniformly mixing the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution and the zinc chloride aqueous solution, regulating the pH value to be 4 by hydrochloric acid, stirring for 2 hours to generate gel, filtering by a 400-mesh screen, washing by a small amount of water, concentrating and drying to obtain a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex;
3g of zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex is added into 35mL of ethanol aqueous solution (obtained by mixing 30mL of deionized water and 5.0mL of ethanol) and stirred for 10min, then 0.1g of NaAlO 2 is added, mixed and stirred until clear, 8mL of ethyl silicate is added dropwise at room temperature and stirred until completely clear, the mixture is left to stand for 6h, crystallized at 110 ℃ for 15h and centrifuged, washed with water until the pH is less than 8, and ethanol is added to prepare 0.5wt.% seed suspension.
(2) 2G of diethylhydroxylamine and 1g of dodecatungstophosphoric acid were mixed with 70mL of deionized water to obtain a diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution, 8mL of ethanol and 5mL of ethyl silicate were sequentially added to the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution and stirred for 4 hours, and then 0.1g of NaAlO 2 and 0.2g of Na 2SO4 were sequentially added and stirred for 1 hour at room temperature to obtain a clear film composition.
(3) Sequentially introducing NaOH solution into a microchannel of a microchannel reactor for alkali treatment for 1h, introducing water for water washing treatment, introducing ethanol solution of 3-aminopropyl trimethoxy silane (the volume ratio of 3-aminopropyl trimethoxy silane to ethanol is 1:10) for 70 ℃ modification treatment for 1.5h, introducing 0.5wt.% seed suspension obtained in the step (1) at the flow rate of 1.55mL/h for 70 ℃ pre-seeding treatment for 1.5h, introducing ethanol for washing and then drying for 1h, introducing the film synthesis solution obtained in the step (2) at the flow rate of 1.55mL/h for 95 ℃ film growth treatment for 3h, introducing water for water washing treatment, and drying for 14h at the temperature of 30 ℃ to obtain the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite film.
The apparatus and the carbon five composition used in the process for producing methyltetrahydrophthalic anhydride were the same as in example 1.
Adding carbon five at 12 ℃ in the first carbon five storage tank 1, carbon five at 22 ℃ in the second carbon five storage tank 3 and carbon five at 32 ℃ in the third carbon five storage tank 5 into 3 micro-channel modules of the micro-channel reactor 9 respectively, wherein the total flow rate of the first advection pump 2, the second advection pump 4 and the third advection pump 6 is 19.56ml/min; maleic anhydride is added into an MA melting tank 7, heated and melted at 62 ℃ for 2.2 hours, and the maleic anhydride after being heated and melted is conveyed into a micro-channel reactor 9 through a high-temperature heating pump 8, wherein the flow rate of the high-temperature heating pump 8 is 8.44ml/min; maleic anhydride in a microchannel reactor 9 with a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of a microchannel sequentially passes through 3 microchannel modules to be pre-reacted with carbon five, the ratio of the total mole number of isoprene and trans-1, 3-pentadiene in the carbon five to the mole number of maleic anhydride is 1.01:1, the pre-reaction temperature is regulated to 65 ℃ by a first cold and hot integrated circulating pump 10, the pre-reaction time is 68s, the back pressure of the system is regulated to 0.4-0.8MPa by a stainless steel cutting sleeve micro-regulating valve 11, materials enter a kettle type reactor 12 to be subjected to secondary reaction at 65 ℃ for 20min after the pre-reaction is finished, the materials enter a separation tank 15 to be separated after the secondary reaction, the separation temperature is 50 ℃, the unreacted carbon five in a gas phase enters a carbon five receiving tank 16, and the liquid-phase product methyl tetrahydrophthalic anhydride enters a finished product tank 17.
The yield of the product methyl tetrahydrophthalic anhydride is 99.28 percent.
Example 3
The preparation method of the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane comprises the following steps:
(1) 77g of diethylhydroxylamine, 48g of dodecatungstophosphoric acid and deionized water to prepare 500g of 25wt.% diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution, 15.336gZnCl 2 and 1250g of water to prepare 0.09mol/L zinc chloride aqueous solution; uniformly mixing the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution and the zinc chloride aqueous solution, regulating the pH value to be 4.5 by hydrochloric acid, stirring for 2 hours to generate gel, filtering by a 400-mesh screen, washing by a small amount of water, concentrating and drying to obtain a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex;
8g of zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex is added into 40mL of ethanol aqueous solution (obtained by mixing 33mL of deionized water and 7.0mL of ethanol) and stirred for 10min, then 0.2g of NaAlO 2 is added, mixed and stirred until clear, 12mL of ethyl silicate is added dropwise at room temperature and stirred until completely clear, the mixture is left to stand for 6h, crystallized at 130 ℃ in a hydrothermal synthesis kettle for 13h and centrifuged, water is washed until the pH is less than 8, and ethanol is added to prepare 2wt.% seed suspension.
(2) 2.5G of diethylhydroxylamine and 1.5g of dodecatungstophosphoric acid were mixed with 70mL of deionized water to obtain a diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution, 10mL of ethanol and 7mL of ethyl silicate were sequentially added to the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution and stirred for 4 hours, and then 0.2g of NaAlO 2 and 0.3g of Na 2SO4 were sequentially added and stirred for 1 hour at room temperature to obtain a clear film composition.
(3) Sequentially introducing NaOH solution into a microchannel of a microchannel reactor for alkali treatment for 2 hours, introducing water for water washing treatment, introducing ethanol solution of 3-aminopropyl trimethoxy silane (the volume ratio of 3-aminopropyl trimethoxy silane to ethanol is 1:20) for modification treatment at 80 ℃ for 1 hour, introducing 2wt.% seed suspension obtained in the step (1) at a flow rate of 1.55mL/h for seed pre-coating treatment at 80 ℃ for 1 hour, introducing ethanol for washing and then drying for 1 hour, introducing film synthesis liquid obtained in the step (2) at a flow rate of 1.55mL/h for film growth treatment at 100 ℃ for 1 hour, introducing water for water washing treatment, and drying at 50 ℃ for 10 hours to obtain the zinc-diethylhydroxylamine-dodecatungsten phosphate zeolite film.
The apparatus and the carbon five composition used in the process for producing methyltetrahydrophthalic anhydride were the same as in example 1.
Adding the carbon five with the temperature of 11 ℃ in the first carbon five storage tank 1, the carbon five with the temperature of 21 ℃ in the second carbon five storage tank 3 and the carbon five with the temperature of 31 ℃ in the third carbon five storage tank 5 into 3 micro-channel modules of the micro-channel reactor 9 respectively, wherein the total flow rate of the first advection pump 2, the second advection pump 4 and the third advection pump 6 is 27.87ml/min; maleic anhydride is added into an MA melting tank 7, heated and melted at 61 ℃ for 2.3 hours, and the maleic anhydride after being heated and melted is conveyed into a micro-channel reactor 9 through a high-temperature heating pump 8, wherein the flow rate of the high-temperature heating pump 8 is 11.68ml/min; maleic anhydride in a microchannel reactor 9 with a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of a microchannel sequentially passes through 3 microchannel modules to be pre-reacted with carbon five, the ratio of the total mole number of isoprene and trans-1, 3-pentadiene in the carbon five to the mole number of maleic anhydride is 1.05:1, the pre-reaction temperature is regulated to be 75 ℃ by a first cold and hot integrated circulating pump 10, the pre-reaction time is 48s, the back pressure of the system is regulated to be 0.4-0.8MPa by a stainless steel cutting sleeve micro-regulating valve 11, materials enter a kettle type reactor 12 to be subjected to 75 ℃ for secondary reaction for 25min after the pre-reaction, the materials enter a separation tank 15 to be separated after the secondary reaction, the separation temperature is 55 ℃, the unreacted carbon five in a gas phase enters a carbon five receiving tank 16, and a liquid-phase product methyl tetrahydrophthalic anhydride enters a finished product tank 17.
The yield of the product methyl tetrahydrophthalic anhydride is 99.51 percent.
Example 4
The procedure of preparation of zinc-diethylhydroxylamine-dodecatungstophosphoric acid zeolite membrane, the apparatus used for the production of methyltetrahydrophthalic anhydride and the composition of carbon five were the same as in example 1.
Adding 10 ℃ of carbon five in the first carbon five storage tank 1, 20 ℃ of carbon five in the second carbon five storage tank 3 and 30 ℃ of carbon five in the third carbon five storage tank 5 into 3 micro-channel modules of the micro-channel reactor 9 respectively, wherein the total flow rate of the first advection pump 2, the second advection pump 4 and the third advection pump 6 is 14.62ml/min; maleic anhydride is added into an MA melting tank 7, heated and melted at 60 ℃ for 2.5 hours, and the maleic anhydride after being heated and melted is conveyed into a micro-channel reactor 9 through a high-temperature heating pump 8, wherein the flow rate of the high-temperature heating pump 8 is 6.34ml/min; maleic anhydride in a microchannel reactor 9 with a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of a microchannel sequentially passes through 3 microchannel modules to be pre-reacted with carbon five, the ratio of the total mole number of isoprene and trans-1, 3-pentadiene in the carbon five to the mole number of maleic anhydride is 1.03:1, the pre-reaction temperature is regulated to be 45 ℃ by a first cold and hot integrated circulating pump 10, the pre-reaction time is 87s, the back pressure of the system is regulated to be 0.4-0.8MPa by a stainless steel cutting sleeve micro-regulating valve 11, materials enter a kettle type reactor 12 to be subjected to secondary reaction at 45 ℃ for 30min after the pre-reaction is finished, the materials enter a separation tank 15 to be separated after the secondary reaction, the separation temperature is 60 ℃, the unreacted carbon five in a gas phase enters a carbon five receiving tank 16, and a liquid-phase product methyl tetrahydrophthalic anhydride enters a finished product tank 17.
The yield of the product methyl tetrahydrophthalic anhydride is 99.62 percent.
Example 5
The procedure of preparation of zinc-diethylhydroxylamine-dodecatungstophosphoric acid zeolite membrane, the apparatus used for the production of methyltetrahydrophthalic anhydride and the composition of carbon five were the same as in example 1.
Adding 10 ℃ of carbon five in the first carbon five storage tank 1, 20 ℃ of carbon five in the second carbon five storage tank 3 and 30 ℃ of carbon five in the third carbon five storage tank 5 into 3 micro-channel modules of the micro-channel reactor 9 respectively, wherein the total flow rate of the first advection pump 2, the second advection pump 4 and the third advection pump 6 is 12.47ml/min; maleic anhydride is added into an MA melting tank 7, heated and melted at 60 ℃ for 2.5 hours, and the maleic anhydride after being heated and melted is conveyed into a micro-channel reactor 9 through a high-temperature heating pump 8, wherein the flow rate of the high-temperature heating pump 8 is 5.37ml/min; maleic anhydride in a microchannel reactor 9 with a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane on the inner surface of a microchannel sequentially passes through 3 microchannel modules to be pre-reacted with carbon five, the ratio of the total mole number of isoprene and trans-1, 3-pentadiene in the carbon five to the mole number of maleic anhydride is 1.04:1, the pre-reaction temperature is regulated to be 35 ℃ by a first cold and hot integrated circulating pump 10, the pre-reaction time is 106s, the back pressure of the system is regulated to be 0.4-0.8MPa by a stainless steel cutting sleeve micro-regulating valve 11, materials enter a kettle type reactor 12 to be subjected to secondary reaction at 35 ℃ for 30min after the pre-reaction is finished, the materials enter a separation tank 15 to be separated after the secondary reaction, the separation temperature is 40 ℃, the unreacted carbon five in a gas phase enters a carbon five receiving tank 16, and a liquid-phase product methyl tetrahydrophthalic anhydride enters a finished product tank 17.
The yield of the product methyl tetrahydrophthalic anhydride is 99.56 percent.
Comparative example 1
In the step (1) of the preparation method of zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane, ethanol was added to prepare 1wt.% seed suspension, and ethanol was added to prepare 0.2wt.% seed suspension, and the other steps were the same as in example 1.
The yield of the product methyl tetrahydrophthalic anhydride is 95.88 percent.
The seed suspension concentration in comparative example 1 was too low compared to example 1, resulting in a decrease in yield of methyltetrahydrophthalic anhydride.
Comparative example 2
In the step (1) of the preparation method of zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane, ethanol was added to prepare 1wt.% seed suspension, and ethanol was added to prepare 3wt.% seed suspension, and the other steps were the same as in example 1.
The yield of the product methyltetrahydrophthalic anhydride is 97.65%.
The seed suspension concentration in comparative example 2 was too high compared to example 1, resulting in a decrease in yield of methyltetrahydrophthalic anhydride.
Comparative example 3
The preparation method of the diethyl hydroxylamine-dodecatungstophosphoric acid zeolite membrane comprises the following steps:
(1) 3.0851g of diethylhydroxylamine and 1.9725g of dodecatungstophosphoric acid are added into 38mL of ethanol aqueous solution (obtained by mixing 32mL of deionized water and 6.0mL of ethanol) and stirred for 10min, 0.1324g of NaAlO 2 is added, mixed and stirred until clear, 10.3mL of ethyl silicate is added dropwise at room temperature and stirred until completely clear, the mixture is left to stand for 6h, after crystallization for 14h at 120 ℃ in a hydrothermal synthesis kettle, the mixture is centrifuged, water is washed until the pH is less than 8, and ethanol is added to prepare 1wt.% seed suspension;
Step (2) and step (3) were conducted in the same manner as in example 1 to obtain a diethylhydroxylamine-dodecatungstophosphoric acid zeolite membrane.
The other steps are the same as in example 1.
The yield of the product methyl tetrahydrophthalic anhydride is 92.26 percent.
The absence of ZnCl 2 in comparative example 3, compared with example 1, leads to the absence of formation of complex systems and to a reduction in the catalytic efficiency, and consequently to a reduction in the yield of methyltetrahydrophthalic anhydride.
Comparative example 4
A zinc-dodecatungstophosphoric acid zeolite membrane was prepared without adding diethylhydroxylamine, and the procedure was the same as in example 1.
The yield of the product methyltetrahydrophthalic anhydride is 96.38%.
In comparative example 4, as compared with example 1, the addition of diethylhydroxylamine was not effective in preventing olefin self-polymerization, resulting in a decrease in yield of methyltetrahydrophthalic anhydride.
Comparative example 5
The preparation method of the zinc-diethyl hydroxylamine zeolite membrane comprises the following steps:
(1) 0.7212gZnCl 2 and 3.0851g of diethylhydroxylamine are added into 38mL of ethanol aqueous solution (obtained by mixing 32mL of deionized water and 6.0mL of ethanol) and stirred for 10min, 0.1324g of NaAlO 2 is added, mixed and stirred until clear, 10.3mL of ethyl silicate is added dropwise at room temperature and stirred until completely clear, the mixture is left to stand for 6h, crystallized in a hydrothermal synthesis kettle at 120 ℃ for 14h and centrifuged, washed with water until the pH is less than 8, and ethanol is added to prepare 1wt.% seed suspension;
step (2) and step (3) were the same as in example 1 to obtain a zinc-diethylhydroxylamine zeolite membrane.
The other steps are the same as in example 1.
The yield of the product methyl tetrahydrophthalic anhydride is 93.02%.
The absence of the addition of dodecatungstophosphoric acid in comparative example 5 resulted in the formation of no complex system and a decrease in catalytic efficiency, and in turn, in a decrease in yield of methyltetrahydrophthalic anhydride, as compared with example 1.
Comparative example 6
The procedure of example 1 was repeated except that 10℃of the first tank 1, 20℃of the second tank 3 and 30℃of the third tank 5 were changed to 10℃of the first tank 1, 10℃of the second tank 3 and 10℃of the third tank 5.
The yield of the product methyltetrahydrophthalic anhydride is 96.93 percent.
Comparative example 7
The procedure of example 1 was repeated except that the 10℃C five in the first C five tank 1, the 20℃C five in the second C five tank 3 and the 30℃C five in the third C five tank 5 were changed to 20℃C five in the first C five tank 1, 20℃C five in the second C five tank 3 and 20℃C five in the third C five tank 5.
The yield of the product methyl tetrahydrophthalic anhydride is 97.19 percent.
Comparative example 8
The procedure of example 1 was repeated except that 10℃of the first tank 1, 20℃of the second tank 3, and 30℃of the third tank 5 were changed to 30℃of the first tank 1, 30℃of the second tank 3, and 30℃of the third tank 5.
The yield of the product methyl tetrahydrophthalic anhydride is 97.58 percent.
The carbon five temperatures in the first, second and third carbon five reservoirs were all the same in comparative examples 6-8, and the reaction efficiency was lower, resulting in a decrease in yield of methyltetrahydrophthalic anhydride, as compared to example 1.
Claims (10)
1. A method for producing methyl tetrahydrophthalic anhydride is characterized in that the inner surface of a micro-channel reactor is sequentially subjected to alkali treatment, modification treatment, pre-coating seed crystal treatment and film growth treatment to obtain the micro-channel reactor with a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite film on the inner surface of the micro-channel; introducing the carbon five and maleic anhydride into a microchannel reactor with a zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite membrane on the inner surface of the microchannel to perform a pre-reaction, then performing a secondary reaction, and separating to obtain the methyltetrahydrophthalic anhydride.
2. The method for producing methyltetrahydrophthalic anhydride according to claim 1, characterized in that the preparation method of the zinc-diethylhydroxylamine-dodecatungsten phosphate zeolite membrane comprises the following steps:
(1) Uniformly mixing a diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution and a zinc chloride aqueous solution, regulating the pH, stirring, filtering, washing with water, concentrating and drying to obtain a zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex; adding zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex into ethanol water solution, stirring, sequentially adding sodium metaaluminate and ethyl silicate, stirring, standing, crystallizing, centrifuging, washing with water, and adding ethanol to obtain seed suspension;
(2) Sequentially adding ethanol and ethyl silicate into the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution, stirring, and sequentially adding sodium metaaluminate and sodium sulfate, stirring to obtain a membrane synthetic solution;
(3) Sequentially introducing alkali liquor into a micro-channel of a micro-channel reactor for alkali treatment, introducing water for water washing treatment, introducing an ethanol solution of an amino silane coupling agent for modification treatment, introducing seed suspension for pre-coating seed crystal treatment, introducing film synthesis liquid for film growth treatment, introducing water for water washing treatment, and drying to obtain the zinc-diethyl hydroxylamine-dodecatungsten phosphate zeolite film.
3. The method for producing methyltetrahydrophthalic anhydride according to claim 2, characterized in that the mass concentration of the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution in step (1) is 15 to 25wt.%, and the mass ratio of diethylhydroxylamine to dodecatungstophosphoric acid in the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution is 2 to 2.4:1.3 to 1.5, wherein the molar concentration of the zinc chloride aqueous solution is 0.01 to 0.09mol/L, and the mass ratio of the diethyl hydroxylamine-dodecatungstophosphoric acid aqueous solution to the zinc chloride aqueous solution is 1:1.5 to 2.6; adjusting the pH to 4-4.5; the ratio of the zinc-diethyl hydroxylamine-dodecatungstophosphoric acid complex to the ethanol aqueous solution to the sodium metaaluminate to the ethyl silicate is 3-8:35-40:0.1-0.2:8-12, wherein the zinc-diethyl hydroxylamine-dodecatungsten phosphate complex and sodium metaaluminate are calculated in g, and the ethanol aqueous solution and the ethyl silicate are calculated in mL; the volume ratio of ethanol and water in the ethanol water solution is 5-7:30-33, the crystallization temperature is 110-130 ℃, the crystallization time is 13-15h, and the concentration of the seed suspension is 0.5-2wt.%.
4. The method for producing methyltetrahydrophthalic anhydride according to claim 2, wherein the ratio of diethylhydroxylamine, dodecatungstophosphoric acid and deionized water in the aqueous diethylhydroxylamine-dodecatungstophosphoric acid solution in step (2) is 2.0-2.5:1.0-1.5:70, wherein, the diethyl hydroxylamine and the dodecatungstophosphoric acid are calculated in g and the deionized water is calculated in mL; the proportion of the diethylhydroxylamine, the ethanol, the ethyl silicate, the sodium metaaluminate and the sodium sulfate in the diethylhydroxylamine-dodecatungstophosphoric acid aqueous solution is 2.0-2.5:8-10:5-7:0.1-0.2:0.2-0.3, wherein, the contents of diethyl hydroxylamine, sodium metaaluminate and sodium sulfate are calculated in g, and the contents of ethanol and ethyl silicate are calculated in mL.
5. The method for producing methyltetrahydrophthalic anhydride according to claim 2, wherein the alkali solution in the step (3) is sodium hydroxide solution, and the alkali treatment time is 1-2 hours; the volume ratio of the amino silane coupling agent to the ethanol in the ethanol solution of the amino silane coupling agent is 1:10-20, wherein the amino silane coupling agent is 3-aminopropyl trimethoxy silane, the modification treatment temperature is 60-80 ℃, and the modification treatment time is 1-2h; the pre-coating seed crystal treatment temperature is 60-80 ℃, and the pre-coating seed crystal treatment time is 1-2h; the film growth treatment temperature is 95-100 ℃, and the film growth treatment time is 1-3h; the drying temperature is 30-50 ℃.
6. The method for producing methyltetrahydrophthalic anhydride according to claim 1, wherein the carbon five composition comprises isoprene and trans-1, 3-pentadiene, and wherein the ratio of the total number of moles of isoprene and trans-1, 3-pentadiene to the number of moles of maleic anhydride in the carbon five composition is 1.01-1.05:1.
7. The method for producing methyltetrahydrophthalic anhydride according to claim 1, wherein the pre-reaction temperature is 35-75 ℃ and the pre-reaction time is 48-106s.
8. The method for producing methyltetrahydrophthalic anhydride according to claim 1, wherein the temperature of the secondary reaction is 35-75 ℃ and the time of the secondary reaction is 20-30min.
9. The process for producing methyltetrahydrophthalic anhydride according to claim 1, characterized in that the separation temperature is 40-60 ℃.
10. The method for producing methyl tetrahydrophthalic anhydride according to any one of claims 1 to 9, characterized in that the apparatus used in the method for producing methyl tetrahydrophthalic anhydride comprises a first carbon five storage tank (1), a second carbon five storage tank (3) and a third carbon five storage tank (5), the first carbon five storage tank (1), the first advection pump (2) and the microchannel reactor (9) are sequentially connected, the second carbon five storage tank (3), the second advection pump (4) and the microchannel reactor (9) are sequentially connected, the third carbon five storage tank (5), the third advection pump (6) and the microchannel reactor (9) are sequentially connected, the microchannel reactor (9), the high-temperature heating pump (8) and the MA melt tank (7) are sequentially connected, the microchannel reactor (9) is sequentially connected with a first cold and hot integrated circulating pump (10), the microchannel reactor (9), the tank reactor (12) and the vacuum pump (14) are sequentially connected with a separating tank (15), a non-integral steel cooling and fine-tuning valve (11) is arranged between the microchannel reactor (9) and the tank reactor (12), and the second pump (16) is respectively connected with the cold and fine-tuning tank (13).
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| US20060257662A1 (en) * | 2003-01-17 | 2006-11-16 | Patrice Bujard | Process for the production of porous inorganic materials or a matrix material containing nanoparticles |
| US20150265975A1 (en) * | 2009-05-21 | 2015-09-24 | Battelle Memorial Institute | Thin-sheet zeolite membrane and methods for making the same |
| CN115572274A (en) * | 2022-11-11 | 2023-01-06 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as raw material |
| CN116393120A (en) * | 2023-03-31 | 2023-07-07 | 浙江大学 | Method and catalyst for preparing D, L-tartaric acid through microchannel reaction |
| US20240024830A1 (en) * | 2020-10-28 | 2024-01-25 | China Petroleum & Chemical Corporation | Liquid-liquid mixer, liquid-liquid reaction apparatus comprising liquid-liquid mixer, and liquid-liquid reaction method using liquid-liquid mixer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060257662A1 (en) * | 2003-01-17 | 2006-11-16 | Patrice Bujard | Process for the production of porous inorganic materials or a matrix material containing nanoparticles |
| US20150265975A1 (en) * | 2009-05-21 | 2015-09-24 | Battelle Memorial Institute | Thin-sheet zeolite membrane and methods for making the same |
| US20240024830A1 (en) * | 2020-10-28 | 2024-01-25 | China Petroleum & Chemical Corporation | Liquid-liquid mixer, liquid-liquid reaction apparatus comprising liquid-liquid mixer, and liquid-liquid reaction method using liquid-liquid mixer |
| CN115572274A (en) * | 2022-11-11 | 2023-01-06 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously co-producing nadic anhydride and methyl tetrahydrophthalic anhydride by using cracking carbon five as raw material |
| CN116393120A (en) * | 2023-03-31 | 2023-07-07 | 浙江大学 | Method and catalyst for preparing D, L-tartaric acid through microchannel reaction |
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