CN109678674B - Preparation method of bisphenol F - Google Patents
Preparation method of bisphenol F Download PDFInfo
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- CN109678674B CN109678674B CN201710974161.4A CN201710974161A CN109678674B CN 109678674 B CN109678674 B CN 109678674B CN 201710974161 A CN201710974161 A CN 201710974161A CN 109678674 B CN109678674 B CN 109678674B
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000007864 aqueous solution Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000005192 partition Methods 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 52
- 239000003729 cation exchange resin Substances 0.000 claims description 33
- 238000005507 spraying Methods 0.000 claims description 32
- 239000011964 heteropoly acid Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000011049 filling Methods 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000006004 Quartz sand Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- -1 phenolic aldehyde Chemical class 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- 239000003456 ion exchange resin Substances 0.000 description 13
- 229920003303 ion-exchange polymer Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method of bisphenol F, which comprises the following steps: the fixed bed tubular reactor is divided into three parts by axially arranging partition plates, wherein an upper feeding section and a discharging section are arranged at two sides of each partition plate, and a lower feeding section is arranged below each partition plate; and the phenol aqueous solution and the formaldehyde aqueous solution enter the reactor from a raw material inlet of an upper feeding section as a feeding material I, the phenol aqueous solution and the nitrogen gas enter the reactor from a raw material inlet of a lower feeding section as a feeding material II, the feeding material I is subjected to condensation reaction on a catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feeding material II from bottom to top for further reaction, a reaction product is discharged from a discharge port of a discharging section, and then the bisphenol F is obtained after separation and purification. The method takes phenol and formaldehyde as raw materials, a fixed bed tubular reactor with a partition plate in the middle is adopted as the reactor, and the feeding mode adopts an upper and lower simultaneous feeding mode. The method has the advantages of simple process, high efficiency, mild conditions, stable catalyst activity and long-period operation.
Description
Technical Field
The invention relates to a method for preparing bisphenol F, in particular to a method for preparing bisphenol F by taking phenol and formaldehyde as raw materials.
Background
Bisphenol F, also known as bis- (hydroxyphenyl) methane, has a molecular formula of C13H12O2, a melting point of 160 ℃, is discolored by ultraviolet light, and is a white leafy crystal. It is a monomer for synthetic material, mainly used for synthesizing epoxy resin, polycarbonate resin, polyester resin and phenolic aldehyde resin, fire-retardant, antioxidant and surfactant, etc. The epoxy resin is a base material of a high-performance composite material, has various types, excellent performance, good adhesion, insulativity, chemical stability and thermal stability, is convenient to cure and operate, and has wide application range. At present, the common epoxy resin mainly comprises glycidyl ether resin, namely bisphenol A type epoxy resin. Bisphenol A epoxy resin is used as a mature product, is developed internationally earlier, has large yield in China, accounts for about 70 percent of the consumption of epoxy resin in China, and is often used as general epoxy resin due to wide applicability. However, the resin has high room temperature viscosity, a diluent is required to be added in the use process, the curing time is long, the curing temperature is high, and the generated volatile matter has great pollution to the environment.
The bisphenol F epoxy resin with a similar structure as the novel epoxy resin not only has most excellent characteristics of bisphenol A epoxy resin, but also has the important viscosity of 1/4-1/7 of bisphenol A resin at room temperature, does not need an additive to reduce the viscosity in use, can be cured at low temperature, expands the application range, and has mechanical properties far superior to that of bisphenol A epoxy resin. The polymer material is more and more emphasized by the military industry, the large-scale ship industry and the wind power industry, and as a novel synthetic material, the polymer material is basically in the research stage at present, the industrial technology is still to be developed, and the polymer material has wide application prospect and great market potential.
The synthesis method of bisphenol F generally adopts acid to catalyze phenol and formaldehyde to generate bisphenol F through condensation reaction, and the acid catalyst adopted is sulfuric acid or phosphoric acid, so that the problems of serious corrosion of equipment, difficult separation, generation of a large amount of inorganic wastewater and the like exist; in recent years, there have been methods for synthesizing bisphenol F using an ionic liquid, a modified resin, a modified zeolite, or the like as a catalyst, but these methods all have problems such as low yield of bisphenol F and poor selectivity. At present, the synthesis process of bisphenol F mainly adopts an intermittent kettle type process, has low production efficiency and high energy consumption, and is not suitable for large-scale industrial production process.
CN104326878A discloses a method for synthesizing bisphenol F by nitric acid-accelerated phosphoric acid catalysis, which uses nitric acid and phosphoric acid as catalysts and uses an organic solvent to participate in the synthesis reaction, and has the problems of corrosion, pollution and difficult separation. CN102584541A discloses a method for preparing bisphenol F by using 1-alkyl-3-methylimidazole acidic ionic liquid, which uses an ionic liquid catalyst, and although the problems of corrosion, pollution and the like do not exist, the catalyst needs to be recycled, the energy consumption is high, the service life of the catalyst is short, and the product yield in the later period of use is low. JP11269113 discloses a method for synthesizing bisphenol F with zeolite molecular sieve as a catalyst; CN 101987812a discloses a method for synthesizing bisphenol F with mesoporous molecular sieves as catalyst, which is easier in product separation and catalyst recovery, but has higher phenolic ratio and reaction temperature, difficult control of reaction, and more side reactions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of bisphenol F. The method takes phenol and formaldehyde as raw materials, a fixed bed tubular reactor with a partition plate in the middle is adopted as the reactor, and the feeding mode adopts an upper and lower simultaneous feeding mode. The method has the advantages of simple process, high efficiency, mild conditions, stable catalyst activity and long-period operation.
The preparation method of the bisphenol F comprises the following steps: the fixed bed tubular reactor is divided into three parts by axially arranging partition plates, wherein an upper feeding section and a discharging section are arranged at two sides of each partition plate, and a lower feeding section is arranged below each partition plate; and the phenol aqueous solution and the formaldehyde aqueous solution enter the reactor from a raw material inlet of an upper feeding section as a feeding material I, the phenol aqueous solution and the nitrogen gas enter the reactor from a raw material inlet of a lower feeding section as a feeding material II, the feeding material I is subjected to condensation reaction on a catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feeding material II from bottom to top for further reaction, a reaction product is discharged from a discharge port of a discharging section, and then the bisphenol F is obtained after separation and purification.
In the method, the length of the partition plate is 1/2-2/3 of the length of the reactor, and the top of the partition plate and two side edges of the partition plate are hermetically connected with the wall of the reactor.
In the method, the molar ratio of the phenolic aldehyde in the feed I is 5: 1-10: 1, preferably 4: 1-6: 1, the total volume airspeed is 0.5-1 h-1Preferably 0.6 to 0.8h-1。
In the method, the volume space velocity of the phenol aqueous solution in the feeding II to the catalyst is 0.1-0.6 h-1Preferably 0.3 to 0.5h-1The molar ratio of nitrogen to phenol is 200-300.
In the method, the concentration of the phenol aqueous solution is 40wt% -50 wt%, and the feeding temperature is 65 ℃; the concentration of the formaldehyde aqueous solution is 36-40 wt%, and the feeding temperature is normal temperature, generally 25-30 ℃.
According to the method, quartz sand is filled at two ends of a reactor, a catalyst is filled in the middle section, and the catalyst in the middle section and the quartz sand are mixed and filled, wherein the granularity range of the quartz sand is 1.0-1.2 mm, and the catalyst accounts for 40-60 v% of the total filling amount.
In the method of the present invention, the reaction conditions of the condensation reaction are as follows: the reaction temperature is 70-100 ℃, and preferably 75-85 ℃; the reaction pressure is 0.1 to 1MPa, preferably 0.3 to 0.6 MPa.
In the method, the catalyst used in the condensation reaction is a supported heteropolyacid catalyst. Wherein the carrier is cation exchange resin, the exchange capacity is 4.4-5.3 mol/kg, the mass content of water is 49-53%, the wet apparent density is 0.75-0.95 g/ml, the wet true density is 1.1-1.3 g/ml, and the particle size range is 0.5-1.0 mm; the active component heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, arsenic tungstic acid, germanium tungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid.
In the method, the preparation method of the supported heteropolyacid catalyst comprises the following steps:
(1) washing the cation exchange resin with deionized water for 3-5 times, and 5-10 minutes each time;
(2) vacuum drying the washed cation exchange resin;
(3) then the obtained cation exchange resin is treated by aqueous solution of heteropoly acid with certain concentration, and the supported heteropoly acid catalyst is obtained after drying and roasting.
In the method, the drying temperature in the step (2) is 70-90 ℃, and the drying time is 4-8 hours; in the step (3), the mass percent concentration of the heteropoly acid aqueous solution is 10-50%; the treatment process of the heteropoly acid aqueous solution comprises the following steps: a. filling cation exchange resin into a fine steel wire mesh bag, wherein the thickness of the mesh bag is 1-5 mm, preferably 2-3 mm, and the mesh bag is flatly paved in an ultrasonic vibrator; b. under the condition that the ultrasonic vibration frequency is 50-60 kHz, spraying a gas-liquid mixture of 30-50% heteropoly acid water solution and nitrogen through an atomizing nozzle to the cation exchange resin, wherein the spraying distance is 0-2 cm, preferably 0.5-1 cm, the spraying pressure is 0.02-0.2 MPa, preferably 0.05-0.1 MPa, and the spraying time is 1-4 h, preferably 2-3 h; c. then drying and roasting the cation exchange resin for later use; d. repeating the operation process of the step b by using 10-20% heteropoly acid aqueous solution, and then drying and roasting the cation exchange resin to obtain a supported heteropoly acid catalyst; wherein the drying temperature is 70-90 ℃, and the drying time is 6-8 h; the roasting temperature is 180-220 ℃, and the roasting time is 8-12 h.
Compared with the prior art, the invention has the following advantages:
(1) the reaction is carried out on a fixed bed continuous reactor with a partition plate, the material is fed in an upper and lower simultaneous feeding mode, the reaction material fed in the upper mode enters the reactor and passes through a catalyst bed layer under a certain airspeed condition, part of reactants firstly react to a certain extent and move downwards, the reaction material fed in the lower mode enters the reactor under a certain airspeed condition, the reaction material is mixed with the material moving downwards and then passes through the catalyst bed layer and moves upwards, the molar proportion of phenol is increased after the materials are mixed, the reaction is further carried out, the condensation reaction conversion rate is improved, catalyst impurities are not contained in the reactants, and the subsequent separation process is facilitated.
(2) The upper feeding and the lower feeding have an airspeed difference (the upper feeding airspeed is greater than the lower feeding airspeed), so that the feeding at the upper end of the reactor passes through the catalyst bed layer in a reciprocating manner, the reaction is more sufficient, and the conversion rate of phenol is improved.
(3) The catalyst filling section is filled by mixing with quartz sand, the lower feeding is the mixed feeding of phenol and nitrogen, and the catalyst is continuously boiled in a gap formed by the quartz sand under the driving action of the nitrogen with certain air flow and air speed, so that the contact probability and mass transfer efficiency of reaction materials and the active center of the catalyst are increased, and the reaction efficiency and the conversion rate are improved.
(4) The axial baffle is added in the reactor, so that the moving path of the feeding material at the inlet I is limited, the process that the feeding material at the inlet I is partially reacted firstly and then is further reacted with the feeding material at the inlet II is realized, the reaction is more sufficient, and the conversion rate is higher.
(5) Under the condition of ultrasonic wave, nitrogen and heteropoly acid solution are used for spraying and treating the catalyst twice, so that tiny impurities in the pore channel of the catalyst are blown out, and meanwhile, active components are more uniform and solid in the loaded pore channel, so that the catalyst has better activity and stability.
Drawings
FIG. 1 is a schematic view of a process for producing bisphenol F of the present invention.
Wherein: 1-phenol and formaldehyde feed; 2-phenol and nitrogen feeds; 3-discharging the reactant; 4-a separator; 5-catalyst bed layer.
Detailed Description
The preparation process of the supported heteropolyacid catalyst of the present invention is specifically described below: firstly, 50-100 g of strong acid cation exchange resin is washed by deionized water for 3-5 times, each time for 5-10 minutes, the washing temperature is 50-70 ℃, and then the strong acid cation exchange resin is placed in a vacuum drying oven to be dried for 6-8 hours at the temperature of 70-90 ℃. Secondly, filling the dried strong-acid cation exchange resin into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying heteropoly acid aqueous solution with a certain concentration and nitrogen to impregnate the resin under the ultrasonic vibration condition by using an atomizing nozzle, wherein the spraying distance is 1-2 cm, the spraying pressure is 0.05-0.1 MPa, and the spraying time is 1-2 h. And thirdly, washing the resin, drying according to the condition of the step one, and roasting for 6-8 hours at the temperature of 200-230 ℃ for later use. And fourthly, treating the resin to be used by using heteropoly acid aqueous solutions with different concentrations according to the method of the second step, and drying and roasting the washed resin according to the conditions of the third step to obtain the supported heteropoly acid catalyst.
The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass unless otherwise specified. The ultrasonic vibrator used in the preparation of the supported heteropolyacid catalyst is KQ-550B, and the atomizing nozzle is JLN-G type high-pressure fine atomizing nozzle, and is purchased from Jining Jun atomizing equipment Co. Ion exchange resin catalysts are available from Special resins, Inc. of Mingzhu, Dendong.
The specific embodiment of the invention is as follows: the method comprises the steps of reacting on a fixed bed continuous reactor with a partition plate, pumping a phenol aqueous solution into the reactor by a lining micro-metering pump, pumping a formaldehyde aqueous solution into the reactor by a high-pressure plunger pump, and feeding in an upper and lower simultaneous feeding mode. The phenol aqueous solution and the formaldehyde aqueous solution which are fed from the upper part are mixed and then react through a catalyst bed layer, the reacted materials further react with the phenol aqueous solution which is fed from the lower part, and the reaction product is discharged from an outlet at the upper part of the reactor.
Example 1
1. Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is placed in a vacuum drying oven to be dried for 4 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 2mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 59kHz, and spraying and soaking 40% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 1cm, and the spraying pressure is 0.05 MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 20% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with a clapboard, the catalyst and quartz sand are mixed and filled in 30ml, and the filling volume ratio is 1: 1; the concentration of the phenol aqueous solution is 40wt%, and the concentration of the formaldehyde aqueous solution is 37 wt%; the reaction temperature is 75 ℃, the reaction pressure is 0.5MPa, and the upper feeding total volume space velocity is 0.6h-1The molar ratio of the phenolic aldehyde is 5: 1; the volume space velocity of the phenol aqueous solution to the catalyst in the lower feeding is 0.3 h-1The molar ratio of nitrogen to phenol was 300 and the reaction results are shown in Table 1.
Example 2
1. Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 58kHz, and spraying and soaking 35% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.07 MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 20% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with a clapboard, the catalyst and quartz sand are mixed and filled in 30ml, and the filling volume ratio is 1: 1; the concentration of the phenol aqueous solution is 40wt%, and the concentration of the formaldehyde aqueous solution is 37 wt%; the reaction temperature is 80 ℃, the reaction pressure is 0.5MPa, and the upper feeding total volume space velocity is 0.6h-1The molar ratio of the phenolic aldehyde is 5: 1; the volume space velocity of the phenol aqueous solution to the catalyst in the lower feeding is 0.3 h-1The molar ratio of nitrogen to phenol was 300 and the reaction results are shown in Table 1.
Example 3
1. Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 57kHz, and spraying and soaking 45% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.06 MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 15% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with a clapboard, the catalyst and quartz sand are mixed and filled in 30ml, and the filling volume ratio is 1: 1; the concentration of the phenol aqueous solution is 40wt%, and the concentration of the formaldehyde aqueous solution is 37 wt%; the reaction temperature is 85 ℃, the reaction pressure is 0.5MPa, and the upper feeding total volume airspeed is 0.6h-1The molar ratio of the phenolic aldehyde is 5:1,; the volume space velocity of the phenol aqueous solution to the catalyst in the lower feeding is 0.3 h-1The molar ratio of nitrogen to phenol was 300 and the reaction results are shown in Table 1.
Example 4
1. Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 58kHz, and spraying and soaking 35% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.05 MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 10% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with a clapboard, the catalyst and quartz sand are mixed and filled in 30ml, and the filling volume ratio is 1: 1; the concentration of the phenol aqueous solution is 45wt%, and the concentration of the formaldehyde aqueous solution is 37 wt%; the reaction temperature is 80 ℃, the reaction pressure is 0.5MPa, and the upper feeding total volume space velocity is 0.8h-1The molar ratio of the phenolic aldehyde is 5: 1; the volume space velocity of the phenol aqueous solution to the catalyst in the lower feeding is 0.3 h-1The molar ratio of nitrogen to phenol was 200 and the reaction results are shown in Table 1.
Example 5
1. Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 56kHz, and spraying and soaking 50% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.07 MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 210 ℃ for 8 hours; d: and then treating the resin with 20% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 200 ℃ to obtain the supported heteropolyacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with a clapboard, the catalyst and quartz sand are mixed and filled in 30ml, and the filling volume ratio is 1: 1; the concentration of the phenol aqueous solution is 45wt%, and the concentration of the formaldehyde aqueous solution is 37 wt%; the reaction temperature is 80 ℃, the reaction pressure is 0.5MPa, and the upper feeding total volume space velocity is 0.8h-1The molar ratio of the phenolic aldehyde is 5: 1; the volume space velocity of the phenol aqueous solution to the catalyst in the lower feeding is 0.5h-1The molar ratio of nitrogen to phenol was 300 and the reaction results are shown in Table 1.
Example 6
1. Preparing a modified ion exchange resin catalyst: a: 150 g of styrene strong acid cation exchange resin is washed by deionized water for 5 times, each time is 10 minutes, and the styrene strong acid cation exchange resin is dried in a vacuum drying oven for 6 hours at the temperature of 90 ℃; b: filling the dried strong-acid cation exchange resin into a steel wire mesh bag with the thickness of 3mm, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the vibration frequency is 58kHz, and spraying and soaking 35% of phosphotungstic acid aqueous solution and nitrogen for 2 hours by using an atomizing nozzle, wherein the spraying distance is 2cm, and the spraying pressure is 0.07 MPa; c: drying in a vacuum drying oven at 90 ℃ for 6 hours after washing, and roasting the dried ion exchange resin at 220 ℃ for 8 hours; d: and then treating the resin with 15% phosphotungstic acid aqueous solution according to the method b, washing, drying in a vacuum drying oven for 6 hours at 80 ℃, and roasting the dried ion exchange resin for 8 hours at 210 ℃ to obtain the supported heteropolyacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with a clapboard, the catalyst and quartz sand are mixed and filled in 30ml, and the filling volume ratio is 1: 1; the concentration of the phenol aqueous solution is 50wt%, and the concentration of the formaldehyde aqueous solution is 37 wt%; the reaction temperature is 80 ℃, the reaction pressure is 0.5MPa, and the upper feeding total volume space velocity is 0.6h-1The molar ratio of the phenolic aldehyde is 6: 1; the volume space velocity of the phenol aqueous solution to the catalyst in the lower feeding is 0.3 h-1The molar ratio of nitrogen to phenol was 200 and the reaction results are shown in Table 1.
Comparative example 1
The catalyst used in the reaction was D005 II type resin catalyst, the other conditions were the same as in example 5, and the reaction results are shown in Table 1.
Comparative example 2
During the reaction, only the feeding mode is adopted, other conditions are the same as example 5, and the reaction results are shown in table 1.
Comparative example 3
In the reaction process, the fixed bed reactor has no partition plate in the middle, other conditions are the same as example 5, and the reaction results are shown in Table 1.
Comparative example 4
During the reaction, only phenol was fed into the bottom feed, nitrogen was not fed into the bottom feed, the other conditions were the same as in example 5, and the reaction results are shown in Table 1.
Comparative example 5
The preparation process of the used catalyst has no ultrasonic vibration and mixed spraying process of the modification liquid and nitrogen, only the catalyst is modified by adopting a conventional supersaturated impregnation method, other conditions are the same as those of the example 5, and the reaction results are shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Claims (10)
1. The preparation method of bisphenol F is characterized by comprising the following steps: the fixed bed tubular reactor is divided into three parts by axially arranging partition plates, wherein an upper feeding section and a discharging section are arranged at two sides of each partition plate, and a lower feeding section is arranged below each partition plate; taking a phenol aqueous solution and a formaldehyde aqueous solution as a feeding material I, feeding the phenol aqueous solution and the nitrogen as a feeding material II into the reactor from a raw material inlet of an upper feeding section, carrying out condensation reaction on the feeding material I in a catalyst bed layer in the middle of the reactor, mixing the reacted material with the feeding material II from bottom to top, further reacting, discharging a reaction product from a discharge port of a discharging section, and then separating and purifying to obtain bisphenol F;
the catalyst used in the condensation reaction is a supported heteropolyacid catalyst, the carrier is cation exchange resin, the exchange capacity is 4.4-5.3 mol/kg, the mass content of water is 49-53%, the wet apparent density is 0.75-0.95 g/ml, the wet true density is 1.1-1.3 g/ml, and the particle size range is 0.5-1.0 mm; the active component heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, arsenic tungstic acid, germanium tungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid;
the preparation method of the supported heteropolyacid catalyst comprises the following steps:
firstly, 50-100 g of strong acid cation exchange resin is washed by deionized water for 3-5 times, each washing time is 5-10 minutes, the washing temperature is 50-70 ℃, and then the strong acid cation exchange resin is placed in a vacuum drying oven to be dried for 6-8 hours at the temperature of 70-90 ℃;
secondly, filling the dried strong-acid cation exchange resin into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying an aqueous solution of 30-50% heteropoly acid and nitrogen to impregnate the resin by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1-2 cm, the spraying pressure is 0.05-0.1 MPa, and the spraying time is 1-2 h;
thirdly, after washing the resin, drying the resin according to the condition of the first step, and roasting the resin for 6 to 8 hours at the temperature of 200 to 230 ℃ for later use;
and fourthly, treating the resin to be used by using a heteropoly acid aqueous solution with the concentration of 10-20% according to the method of the second step, washing, drying and roasting according to the conditions of the third step to obtain the supported heteropoly acid catalyst.
2. The method of claim 1, wherein: the length of the partition plate is 1/2-2/3 of the length of the reactor.
3. The method of claim 1, wherein: the phenolic aldehyde molar ratio in the feeding I is 5: 1-10: 1, and the total volume airspeed is 0.5-1 h-1。
4. A method according to claim 3, characterized by: the total volume airspeed of the feeding I is 0.6-0.8 h-1。
5. The method of claim 1, wherein: the volume space velocity of the phenol aqueous solution in the feeding II to the catalyst is 0.1-6 h-1。
6. The method of claim 5, wherein: the volume space velocity of the phenol aqueous solution in the feeding II to the catalyst is 0.3-0.5 h-1。
7. The method of claim 1, wherein: and the air inflow of the nitrogen in the feeding II is 200-300L/h.
8. The method of claim 1, wherein: the concentration of the phenol aqueous solution is 40wt% -50 wt%, and the concentration of the formaldehyde aqueous solution is 36wt% -40 wt%.
9. The method of claim 1, wherein: the filling method of the catalyst comprises the steps of filling quartz sand at two ends of a reactor, filling the catalyst at the middle section, and filling the catalyst and the quartz sand in the middle section in a mixed manner, wherein the granularity range of the quartz sand is 1.0-1.2 mm, and the catalyst accounts for 40-60 v% of the total filling amount.
10. The method of claim 1, wherein: the reaction conditions for the condensation reaction were as follows: the reaction temperature is 70-100 ℃, and the reaction pressure is 0.1-1 MPa.
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