CN114685249A - Preparation method of o-phenylphenol - Google Patents
Preparation method of o-phenylphenol Download PDFInfo
- Publication number
- CN114685249A CN114685249A CN202011612844.3A CN202011612844A CN114685249A CN 114685249 A CN114685249 A CN 114685249A CN 202011612844 A CN202011612844 A CN 202011612844A CN 114685249 A CN114685249 A CN 114685249A
- Authority
- CN
- China
- Prior art keywords
- phenylphenol
- cation exchange
- bipolar
- membrane
- membranes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 235000010292 orthophenyl phenol Nutrition 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000012528 membrane Substances 0.000 claims abstract description 112
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000005341 cation exchange Methods 0.000 claims abstract description 44
- 230000020477 pH reduction Effects 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 238000000909 electrodialysis Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003208 petroleum Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000003011 anion exchange membrane Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 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 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 o-phenylphenol alkali metal salt Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000532 dioxanyl group Chemical group 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910006715 Li—O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Mixing dibenzofuran as a raw material with dioxane as a solvent, adding an alkali metal catalyst, stirring and heating under the protection of inert gas for reaction, distilling the reaction mixture to recover dioxane, adding water into residues, filtering and recovering unreacted raw materials, transferring water-phase filtrate to a bipolar membrane electrodialyzer for electrodialysis to separate out a crude product of the o-phenylphenol, and adding petroleum ether into the crude product of the o-phenylphenol for recrystallization to obtain a refined o-phenylphenol product. The invention utilizes the bipolar membrane electrodialyzer to electrolyze water to generate H+Realizes the acidification process of the o-phenylphenol alkali metal salt without adding acid liquor, and alkali metal ions generated after acidification migrate out of the acidification under the action of an electric fieldThe mass transfer of the acidification process can be strengthened, the product yield is improved, and the alkaline liquor can be co-produced by utilizing a plurality of groups of bipolar membranes and monovalent cation exchange membranes, so that the operation is convenient and simple, the corrosion to equipment is avoided, and the environmental protection risk is avoided.
Description
Technical Field
The invention relates to a preparation method of o-phenylphenol, in particular to a method for acidification treatment in the production process of o-phenylphenol.
Background
The o-phenylphenol (OPP) is mainly applied to the fields of sterilization and corrosion prevention of fruits and industrial materials, synthesis of novel phosphorus flame retardants, plastic heat stabilizers, antioxidants, plasticizers and the like. By 2019, the total global o-phenylphenol energy can be about 6.2 ten thousand tons/year, and the global o-phenylphenol consumption is about 5.8 ten thousand tons/year.
The mainstream production process of o-phenylphenol in the market at present is a cyclohexanone dimerization dehydrogenation process. The process takes cyclohexanone as a raw material, firstly, the cyclohexanone is polymerized under the action of an acid catalyst to generate a dimer, and then, the dimer is polymerized under the action of a dehydrogenation catalyst to generate o-phenylphenol. The dehydrogenation step of the process needs to be carried out at a high temperature of more than 300 ℃, the energy consumption is large, and the reaction activity and selectivity can only be maintained for hundreds of hours by adopting a noble metal catalyst with high cost.
With the rapid development of the coal chemical industry, it becomes possible to separate dibenzofuran (commonly called dibenzofuran, DBF) from coal tar, and then the production of o-phenylphenol from dibenzofuran is a competitive o-phenylphenol production technical route.
At present, two main process routes for producing o-phenylphenol by using dibenzofuran as a raw material are provided. A catalytic hydrogenation process, namely producing o-phenylphenol by one-step hydrogenolysis of dibenzofuran. However, in the catalytic hydrogenation process, aromatic ring hydrogenation is easier than hydrogenolysis, and thus it is difficult to control o-phenylphenol not to react further. In order to prevent the product from further reaction, the catalytic processing technology needs to be carried out under the conditions of high temperature, low pressure and the like which are not beneficial to aromatic ring hydrogenation. For example, US4000203 and US3989761 disclose a method for producing o-phenylphenol using noble metals as catalysts, respectively, which has a product selectivity of up to 92%, and a conversion of only 25% due to the reaction at high temperature and low pressure, and has a disadvantage of low per pass yield. In addition, the catalytic hydrogenation process also has the defects of high catalyst cost and large energy consumption for separating products of a raw material recycling machine.
Another process for producing o-phenylphenol by using dibenzofuran as initial raw material is alkali metal catalysisThe first of these is found in the literature (h. Gilman, j. Am. chem. soc., 75, 1953, 2947). This document reports that o-phenylphenol can be produced by reacting dibenzofuran with metallic Li in dioxane. The reaction needs to be realized through two steps: the first step is that dibenzofuran opens an aromatic ring-oxygen bond under the action of metal Li to form a Li-O bond and an aromatic ring-Li bond; the second step is to acidify the resulting metalorganic intermediate with H+The substitution of the alkali metal ultimately produces o-phenylphenol. Later, there were reports in the literature that metals which can open one aromatic ring-oxygen bond of dibenzofuran also include metallic sodium (CN 103319313, JP57095931, US 2862035) and sodium hydride (JP 56020533).
Compared with the catalytic hydrogenation process, the alkali metal catalytic process has the advantage of mild reaction conditions. The reaction can be carried out under reaction conditions of atmospheric pressure, below 80 ℃, as disclosed in CN 103319313. However, the existing alkali metal catalysis process comprises a concentrated acid acidification step, has higher requirements on corrosion resistance of equipment, not only increases equipment investment, but also has the problems of treatment of waste acid and salt and the like.
Disclosure of Invention
In order to solve the problem of acidification corrosion of the process for preparing o-phenylphenol by catalyzing dibenzofuran with alkali metal in the prior art, the invention provides a preparation method of o-phenylphenol, which does not need additional acid acidification, improves the product yield and coproduces alkali liquor.
The technical purpose is realized by the following technical scheme:
mixing dibenzofuran as a raw material with dioxane as a solvent, adding an alkali metal catalyst, stirring and heating under the protection of inert gas for reaction, distilling the reaction mixture to recover dioxane, adding water into residues, filtering and recovering unreacted raw materials, transferring water-phase filtrate to a bipolar membrane electrodialyzer for electrodialysis to separate out a crude product of the o-phenylphenol, and adding petroleum ether into the crude product of the o-phenylphenol for recrystallization to obtain a refined o-phenylphenol product.
Further, the bipolar membrane electrodialyzer consists of a positive electrode, a negative electrode, a bipolar membrane and a monovalent cation exchange membrane, at least one group of the bipolar membrane and the monovalent cation exchange membrane are sequentially arranged between the positive electrode and the negative electrode, a compartment formed between the anion exchange membrane and the positive electrode of the bipolar membrane is a polar chamber, a compartment formed between the cation exchange membrane and the monovalent cation exchange membrane of the bipolar membrane is an acidification chamber, and electrolyte washing liquid is introduced into the polar chamber; introducing the aqueous phase filtrate into the acidification chamber; starting the electrodialysis device, and discharging from the acidification chamber to obtain the o-phenylphenol.
The principle of using the bipolar membrane electrodialyzer to separate out the crude product of o-phenylphenol is as follows: h generated by electrolyzing water in bipolar membrane+The cation exchange membrane penetrating through the bipolar membrane enters an acidification chamber, the cation exchange membrane and the o-phenylphenol alkali metal salt in the water phase filtrate are acidified to generate o-phenylphenol, and alkali metal ions migrate out of the acidification chamber through the monovalent cation exchange membrane under the migration of an electric field; and stopping electrodialysis when the pH value of the polar water effluent of the polar chamber is reduced.
Further, stopping electrodialysis when the pH value of the effluent of the polar chamber is 7-7.5.
Further, the bipolar membrane electrodialyzer consists of a positive electrode, a negative electrode, at least two groups of bipolar membranes and at least two groups of monovalent cation exchange membranes, wherein the positive electrode, the bipolar membranes, the monovalent cation exchange membranes, … … and the negative electrode are sequentially arranged between the positive electrode and the negative electrode in sequence, the bipolar membranes and the monovalent cation exchange membranes are alternately arranged between the positive electrode and the negative electrode, and the anion exchange membranes of the bipolar membranes are always closer to the positive electrode than the cation exchange membranes; a compartment formed between the previous group of monovalent cation exchange membranes and the next group of bipolar membranes which are adjacent is an alkali liquor chamber, and alkali liquor is obtained after discharging; namely at least two groups of bipolar membranes and at least two groups of monovalent cation exchange membranes can co-produce alkali liquor.
Furthermore, the bipolar membrane and the monovalent cation exchange membrane are attached to a partition plate with a flow channel, and the partition plate plays a role in supporting and guiding the membranes.
Furthermore, the operating voltage of the electrodialyzer is 0.5-2.0V/membrane pair, and the electrolyte flushing liquid introduced into the polar chamber is selected from LiCl and LiNO3NaCl and NaNO3At least one of the components of the solution,the flow rate is 1-5L/h.
Further, the acidification chamber has a stirring function.
Further, the alkali metal catalyst is metallic lithium and/or metallic sodium.
Further, the inert gas is N2And/or He.
Further, the reaction temperature is 60-90 ℃, and the reaction time is 4-8 h.
Further, the distillation is to collect fractions at 100-102 ℃.
Compared with the prior art, the invention utilizes the bipolar membrane electrodialyzer to electrolyze water to generate H+The method has the advantages that the acidification process of the o-phenylphenol alkali metal salt is realized, no acid liquor needs to be added, alkali metal ions generated after acidification migrate out of the acidification chamber under the action of an electric field, the mass transfer of the acidification process can be strengthened, the product yield is improved, meanwhile, alkali liquor can be co-produced by utilizing multiple groups of bipolar membranes and monovalent cation exchange membranes, the operation is convenient and simple, the corrosion to equipment is avoided, and the environmental protection risk is avoided.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic view of a bipolar membrane electrodialyzer used in the example;
wherein: 1. the positive electrode 2, the anion exchange membrane of the bipolar membrane I, 3, the cation exchange membrane of the bipolar membrane I, 4, the monovalent cation exchange membrane I, 5, the anion exchange membrane of the bipolar membrane II, 6, the cation exchange membrane of the bipolar membrane II, 7, the monovalent cation exchange membrane II, 8, the negative electrode, A is electrolyte washing liquid, and B is water.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The bipolar membrane electrodialyzer device used in the following examples comprises two sets of bipolar membranes and monovalent cation exchange membranes as shown in fig. 1, and specifically, a bipolar membrane i, a monovalent cation exchange membrane i 4, a bipolar membrane ii, and a monovalent cation exchange membrane ii 7 are sequentially arranged between a positive electrode 1 and a negative electrode 8 of the bipolar membrane electrodialyzer. Between anion exchange membrane 2 and the positive pole of bipolar membrane I, be the polar chamber between monovalent cation exchange membrane II 7 and the negative pole, be two independent acidizing rooms between cation exchange membrane 3 and the monovalent cation exchange membrane I4 of bipolar membrane I, between cation exchange membrane 6 and the monovalent cation exchange membrane II 7 of bipolar membrane II respectively, be the alkali lye room between monovalent cation exchange membrane I4 and the anion exchange membrane 5 of bipolar membrane II. The permselectivity of the two monovalent cation exchange membranes was 94%. The bipolar membrane I, the monovalent cation exchange membrane I4, the bipolar membrane II and the monovalent cation exchange membrane II 7 are all attached to the partition board with the flow channel.
The following reaction takes place in the acidification chamber:
acidification of the alkali metal salt of ortho-phenylphenol was carried out using a bipolar membrane electrodialyzer as shown in FIG. 1: after the bipolar membrane electrodialysis device is electrified, electrolytic water reaction is generated in the bipolar membrane, and H generated by electrolysis+Enters an acidification chamber through a bipolar membrane cation exchange membrane to perform acidification reaction with an alkali metal salt of OPP, H+Substituting alkali metal ions to generate OPP, transferring monovalent alkali metal ions out of the acidification chamber through a monovalent cation exchange membrane under the action of an electric field to enable acidification reaction to be continuously carried out in a forward direction, and transferring monovalent alkali metal cations out of the acidification chamber to permeate and OH from an anion exchange layer of the bipolar membrane-And (3) forming dilute alkali liquor in the alkali liquor chamber and flowing out of the electrodialysis device, introducing a flushing fluid A into a polar chamber of the electrodialysis device, and introducing water B into the alkali liquor chamber.
Example 1
17g of dibenzofuran, 70mL of dioxane and 4.6g of metallic sodium are added into a 100mL reaction kettle, nitrogen is flushed into the kettle, air is replaced by clean air, and the reaction is stirred at 90 ℃ for 4 hours. Cooling the reaction mixture to room temperature, transferring the reaction mixture to a round-bottom flask for distillation, and collecting a fraction (the solvent is dioxane) at the temperature of 100-102 ℃; and cooling the bottom liquid of the kettle to room temperature, adding 200mL of deionized water, stirring, carrying out vacuum filtration, recovering the unreacted raw material dibenzofuran (insoluble in water), and transferring the filtrate to an acidification chamber of a bipolar membrane electrodialyzer. Deionized water is used to prepare 0.5mol/L NaCl solution which is introduced into the polar chamber, the flow rate of the polar chamber solution is 2L/h, and the operating voltage of the electrodialyzer is 0.5V/membrane pair. The compartment effluent was checked and the electrodialysis was stopped at pH = 7.0. The suspension in the acidification chamber was removed, filtered, the solid filter cake collected and 20mL of petroleum ether added to it for recrystallization to give 14.7g of o-phenylphenol in 86.4% yield.
Example 2
17g of dibenzofuran, 70mL of dioxane and 4.6g of metallic sodium are added into a 100mL reaction kettle, nitrogen is flushed into the kettle, air is replaced by clean air, and the reaction is stirred at 80 ℃ for 6 hours. Cooling the reaction mixture to room temperature, transferring the reaction mixture to a round-bottom flask for distillation, and collecting a fraction (the solvent is dioxane) at the temperature of 100-102 ℃; and cooling the bottom liquid of the kettle to room temperature, adding 200mL of deionized water, stirring, carrying out vacuum filtration, recovering the unreacted raw material dibenzofuran (insoluble in water), and transferring the filtrate to an acidification chamber of a bipolar membrane electrodialyzer. Deionized water is used to prepare 0.5mol/L NaCl solution which is introduced into the polar chamber, the flow rate of the polar chamber solution is 5L/h, and the operating voltage of the electrodialyzer is 2.0V/membrane pair. The compartment effluent was checked and the electrodialysis was stopped at pH = 7.5. The suspension in the acidification chamber was removed, filtered, the solid filter cake collected and 20mL of petroleum ether added to it for recrystallization to give 14.5g of o-phenylphenol in 85.1% yield.
Example 3
17g of dibenzofuran, 70mL of dioxane and 0.7g of metallic lithium were added to a 100mL reaction kettle, helium was added to the kettle, air was replaced with clean air, and the reaction was stirred at 90 ℃ for 4 hours. Cooling the reaction mixture to room temperature, transferring the reaction mixture to a round-bottom flask for distillation, and collecting a fraction (the solvent is dioxane) at the temperature of 100-102 ℃; and cooling the bottom liquid of the kettle to room temperature, adding 100mL of deionized water, stirring, carrying out vacuum filtration, recovering the unreacted raw material dibenzofuran (insoluble in water), and transferring the filtrate to an acidification chamber of a bipolar membrane electrodialyzer. Preparing 1.0mol/L LiCl solution by deionized water, and introducing the LiCl solution into a polar chamber, wherein the flow rate of the solution in the polar chamber is 3L/h, and the operating voltage of the electrodialyzer is 0.7V/membrane pair. The compartment effluent was checked and the electrodialysis was stopped at pH = 7.2. The suspension in the acidification chamber was removed, filtered, the solid filter cake collected and 20mL of petroleum ether added to it for recrystallization to give 14.8g of o-phenylphenol in 87.1% yield.
Example 4
A100 mL reaction vessel was charged with 17g of dibenzofuran, 70mL of dioxane, and 0.7g of metallic lithium, purged with nitrogen, purged with air, and reacted at 70 ℃ for 7 hours with stirring. Cooling the reaction mixture to room temperature, transferring the reaction mixture to a round-bottom flask for distillation, and collecting a fraction (the solvent is dioxane) at the temperature of 100-102 ℃; and cooling the bottom liquid of the kettle to room temperature, adding 100mL of deionized water, stirring, carrying out vacuum filtration, recovering the unreacted raw material dibenzofuran (insoluble in water), and transferring the filtrate to an acidification chamber of a bipolar membrane electrodialyzer. 1.0mol/L LiNO3 solution prepared by deionized water is introduced into the polar chamber, the flow rate of the polar chamber solution is 4L/h, and the operating voltage of the electrodialyzer is 1.5V/membrane pair. The compartment effluent was checked and the electrodialysis was stopped at pH = 7.0. The suspension in the acidification chamber was removed, filtered, the solid filter cake collected and 20mL of petroleum ether added to it for recrystallization to give 13.7g of o-phenylphenol in 80.5% yield.
Example 5
17g of dibenzofuran, 70mL of dioxane and 4.6g of metallic sodium are added into a 100mL reaction kettle, helium is added into the kettle, air is replaced by clean air, and the mixture is stirred and reacted for 8 hours at the temperature of 60 ℃. Cooling the reaction mixture to room temperature, transferring the reaction mixture to a round-bottom flask for distillation, and collecting a fraction (the solvent is dioxane) at the temperature of 100-102 ℃; and cooling the bottom liquid of the kettle to room temperature, adding 200mL of deionized water, stirring, carrying out vacuum filtration, recovering the unreacted raw material dibenzofuran (insoluble in water), and transferring the filtrate to an acidification chamber of a bipolar membrane electrodialyzer. Deionized water is used for preparing 0.5mol/L NaNO3 solution and then the solution is introduced into a polar chamber, the flow rate of the solution in the polar chamber is 1L/h, and the operating voltage of the electrodialyzer is 1.0V/membrane pair. The compartment effluent was checked and the electrodialysis was stopped at pH = 7.1. The suspension in the acidification chamber was removed, filtered, the solid filter cake collected and 20mL of petroleum ether added to it for recrystallization to give 12.7g of o-phenylphenol in 74.9% yield.
Comparative example 1
17g of dibenzofuran, 70mL of dioxane and 4.6g of metallic sodium are added into a 100mL reaction kettle, nitrogen is flushed into the kettle, air is replaced by clean air, and the reaction is stirred at 80 ℃ for 6 hours. Cooling the reaction mixture to room temperature, transferring the reaction mixture to a round-bottom flask for distillation, and collecting a fraction (the solvent is dioxane) at the temperature of 100-102 ℃; cooling the bottom liquid to room temperature, adding 200mL of deionized water, stirring, carrying out vacuum filtration, recovering unreacted raw material dibenzofuran (insoluble in water), adjusting the pH of the water phase to be less than 3 by using concentrated hydrochloric acid, adding ethyl acetate for extraction, drying by using anhydrous sodium sulfate, removing the solvent under reduced pressure, and recrystallizing petroleum ether to obtain 14.0g of o-phenylphenol with the yield of 82.0%.
Claims (11)
1. A method for preparing o-phenylphenol, which is characterized by comprising the following steps: mixing dibenzofuran serving as a raw material and dioxane serving as a solvent, adding an alkali metal catalyst, stirring and heating under the protection of inert gas for reaction, distilling the reaction mixture to recover dioxane, adding water into residues, filtering and recovering unreacted raw materials, transferring water-phase filtrate to a bipolar membrane electrodialyzer for electrodialysis to separate out an o-phenylphenol crude product, and adding petroleum ether into the o-phenylphenol crude product for recrystallization to obtain a refined o-phenylphenol product.
2. The production process according to claim 1, wherein the bipolar membrane electrodialyzer is composed of positive and negative electrodes, a bipolar membrane and a monovalent cation exchange membrane, at least one set of the bipolar membrane and the monovalent cation exchange membrane being arranged in this order from the positive electrode to the negative electrode, the compartment formed between the anion exchange membrane and the positive electrode of the bipolar membrane being a compartment, the compartment formed between the cation exchange membrane and the monovalent cation exchange membrane of the bipolar membrane being an acidification compartment, an electrolyte rinse solution being introduced into the compartment; introducing the aqueous phase filtrate into the acidification chamber; starting the electrodialysis device, and discharging from the acidification chamber to obtain the o-phenylphenol.
3. The preparation method according to claim 2, wherein the electrodialysis is stopped when the pH of the effluent of the polar chamber is 7-7.5.
4. The production process according to claim 2, wherein the bipolar membrane electrodialyzer is composed of positive and negative electrodes, at least two sets of bipolar membranes, and at least two sets of monovalent cation exchange membranes, in order from the positive electrode to the negative electrode, the bipolar membranes, the monovalent cation exchange membranes, … …, the negative electrode, the bipolar membranes, the monovalent cation exchange membranes being alternately arranged from the positive electrode to the negative electrode, the anion exchange membranes of the bipolar membranes always being closer to the positive electrode than the cation exchange membranes; and a compartment formed between the adjacent previous group of monovalent cation exchange membranes and the next group of bipolar membranes is an alkali liquor chamber, and discharging to obtain alkali liquor.
5. The production method according to claim 2, wherein the bipolar membrane and the monovalent cation exchange membrane are attached to a flow-path separator.
6. The process according to claim 1, wherein the electrodialyzer is operated at a voltage of 0.5 to 2.0V per membrane pair.
7. The method of claim 2, wherein the electrolyte rinse solution introduced into the chamber is selected from the group consisting of LiCl and LiNO3NaCl and NaNO3At least one of the solutions has a flow rate of 1-5L/h.
8. The method of claim 1, wherein the acidification chamber is provided with a stirring function.
9. The method according to claim 1, wherein the alkali metal catalyst is metallic lithium and/or metallic sodium, and the inert gas is N2And/or He.
10. The preparation method according to claim 1, wherein the reaction temperature is 60-90 ℃ and the reaction time is 4-8 h.
11. The preparation method according to claim 1, wherein the distillation is to collect a fraction at 100-102 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011612844.3A CN114685249A (en) | 2020-12-31 | 2020-12-31 | Preparation method of o-phenylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011612844.3A CN114685249A (en) | 2020-12-31 | 2020-12-31 | Preparation method of o-phenylphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114685249A true CN114685249A (en) | 2022-07-01 |
Family
ID=82132294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011612844.3A Pending CN114685249A (en) | 2020-12-31 | 2020-12-31 | Preparation method of o-phenylphenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114685249A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514638A (en) * | 2023-05-09 | 2023-08-01 | 信诺立兴(沧州渤海新区)化工有限公司 | Separation method of byproduct sodium methoxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234961A (en) * | 2008-03-04 | 2008-08-06 | 江苏道森生物化学有限公司 | Method for preparing lactic acid by applying double pole film electrodialysis technique |
| CN103319313A (en) * | 2013-07-18 | 2013-09-25 | 辽宁石化职业技术学院 | Method for preparing o-phenyl phenol by ring opening of dibenzofuran |
| CN105964145A (en) * | 2016-06-17 | 2016-09-28 | 中国科学技术大学 | Method for producing water-insoluble organic acid by bipolar membrane electrodialysis |
| CN106630040A (en) * | 2016-12-28 | 2017-05-10 | 中国科学技术大学 | Selective bipolar membrane electrodialysis system and application thereof |
| CN109721573A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of epoxychloropropane synthetic method |
-
2020
- 2020-12-31 CN CN202011612844.3A patent/CN114685249A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234961A (en) * | 2008-03-04 | 2008-08-06 | 江苏道森生物化学有限公司 | Method for preparing lactic acid by applying double pole film electrodialysis technique |
| CN103319313A (en) * | 2013-07-18 | 2013-09-25 | 辽宁石化职业技术学院 | Method for preparing o-phenyl phenol by ring opening of dibenzofuran |
| CN105964145A (en) * | 2016-06-17 | 2016-09-28 | 中国科学技术大学 | Method for producing water-insoluble organic acid by bipolar membrane electrodialysis |
| CN106630040A (en) * | 2016-12-28 | 2017-05-10 | 中国科学技术大学 | Selective bipolar membrane electrodialysis system and application thereof |
| CN109721573A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of epoxychloropropane synthetic method |
Non-Patent Citations (3)
| Title |
|---|
| 冯红艳等: "《化学工程实验》", vol. 1, 31 January 2014, 中国科学技术大学, pages: 132 - 135 * |
| 董恒等: "双极膜电渗析技术的研究进展", 化工进展, vol. 29, no. 02, 31 December 2010 (2010-12-31), pages 217 - 222 * |
| 赵连俊: "邻苯基苯酚的合成与应用研究进展", 广州化工, vol. 37, no. 03, 31 December 2009 (2009-12-31), pages 61 - 63 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514638A (en) * | 2023-05-09 | 2023-08-01 | 信诺立兴(沧州渤海新区)化工有限公司 | Separation method of byproduct sodium methoxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11131028B2 (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| EP3149228B1 (en) | Method for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| US4950368A (en) | Method for paired electrochemical synthesis with simultaneous production of ethylene glycol | |
| CA2950294C (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| EP0944747B1 (en) | Preparation of onium hydroxides in an electrochemical cell | |
| CN114685249A (en) | Preparation method of o-phenylphenol | |
| WO1998044169A1 (en) | Synthesis of onium hydroxides from onium salts | |
| MX2015000246A (en) | Method for obtaining vanillin from aqueous basic compositions containing vanillin. | |
| CN109354580B (en) | Preparation method of donepezil hydrochloride | |
| JPH07110764B2 (en) | Method for producing alkali metal hypophosphite | |
| JPH09170092A (en) | Preparation of alcoholate | |
| US4640750A (en) | Process for the preparation of 3-hydroxy-3-methylglutaric acid | |
| US3509031A (en) | Electrochemical oxidation of phenol | |
| CA2043256A1 (en) | Electrochemical synthesis and simultaneous purification process | |
| US3937741A (en) | Production of hydroquinone | |
| US4666570A (en) | Process for producing aromatic compound with functional groups | |
| EP0646042B1 (en) | Electrochemical method for the preparation of adipic acid | |
| EP0646107B1 (en) | Method for the simultaneous preparation of dicarboxylic acids and diamines from polyamides | |
| CA2034351A1 (en) | Process for the isolation and purification of free acids, starting from their salts, by electrodialysis | |
| EP0250103B1 (en) | Processfor recovering noble metal | |
| CA2138024C (en) | Simultaneous production of dicarboxylic acids and diamines by splitting polyamides into their monomeric constituents | |
| CN115057800B (en) | Clean synthesis method of p-styrene sulfonate | |
| USRE28203E (en) | Process of producing citric acid | |
| JPH1121689A (en) | Production of high-purity silver | |
| DE3721474A1 (en) | METHOD FOR PRODUCING HEXADIINE (2,4) -DIOL-1,6 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240103 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TA01 | Transfer of patent application right |