CN102659729A - Method for preparing dibenzofuran - Google Patents
Method for preparing dibenzofuran Download PDFInfo
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- CN102659729A CN102659729A CN2012101461970A CN201210146197A CN102659729A CN 102659729 A CN102659729 A CN 102659729A CN 2012101461970 A CN2012101461970 A CN 2012101461970A CN 201210146197 A CN201210146197 A CN 201210146197A CN 102659729 A CN102659729 A CN 102659729A
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- China
- Prior art keywords
- oxide
- diphenylene
- catalyst
- catalyzer
- trichlorine
- Prior art date
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- -1 alkali-metal nitrite Chemical class 0.000 claims description 20
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010970 precious metal Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 238000004873 anchoring Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004304 potassium nitrite Substances 0.000 claims description 6
- 235000010289 potassium nitrite Nutrition 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000009466 transformation Effects 0.000 abstract description 12
- WJURXKWTCOMRCE-UHFFFAOYSA-N 2,4,8-trichlorodibenzofuran Chemical compound C1=C(Cl)C=C2C3=CC(Cl)=CC=C3OC2=C1Cl WJURXKWTCOMRCE-UHFFFAOYSA-N 0.000 abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 27
- 238000005303 weighing Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- 230000024883 vasodilation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing dibenzofuran. The method comprises the following steps of: performing hydrodechlorination on 2,4,8-trichlorodibenzofuran in a kettle reactor at a certain temperature under the normal pressure to obtain dibenzofuran; and reacting by taking aromatic hydrocarbon as a solvent and adding sufficient alkali solution and a phase transfer catalyst under the action of a noble metal loaded catalyst under the condition that the reaction temperature is 40-100 DEG C and the hydrogen flow rate is 10-100 mL/min for 0.5-6 hours to synthesize dibenzofuran. The transformation ratio of 2,4,8-trichlorodibenzofuran is 99.96 percent, and the yield of dibenzofuran is 99.57 percent.
Description
Technical field
The present invention relates to a kind of at tank reactor, under normal pressure and lower temperature conditions, 2,4,8-trichlorine diphenylene-oxide hydrodechlorination prepares the method for diphenylene-oxide, belongs to technical field of chemical engineering.
Background technology
Diphenylene-oxide is a kind of good high boiling organic solvent; Can dissolve multiple macromolecular compound; The raw material that also can be used for medicine, sterilizing agent, sanitas, fuel, synthetic resins and high temperature lubricant has anti-inflammatory, pain relieving, loosening all muscles and vasodilation isoreactivity like some verivates of diphenylene-oxide.In addition, diphenylene-oxide also can form eutectic mixture with biphenyl and uses as the heat transfer solvent.
In the patent of US 4009185A, the employing phenyl ether is a reaction raw materials, and being carried on different carriers with cerium is catalyzer; Diphenylene-oxide is synthesized in continuous oxidation on fixed bed under higher temperature and pressure; Its temperature of reaction is 400-600 ℃, and pressure is 0.1-100atm, and air speed is 1-2000h
-1, the selectivity of diphenylene-oxide is 92%.
In the patent of US 4362883A, the employing phenyl ether is a reaction raw materials, is catalyzer with the carboxylate salt of palladium and the carboxylate salt of copper; In lower oxygen pressure and temperature, and under the carboxylic acid condition in reaction kettle the synthetic diphenylene-oxide of oxidation step, the carboxylate salt of its palladium and copper is the carboxylate salt of 1-4 carbon; Carboxylic acid is the carboxylic acid of 1-5 carbon, and the charge capacity of palladium is 0.5-5%, and the charge capacity of copper is 0.5-5%; Temperature of reaction is 120-140 ℃; Reaction pressure is 26.4-136atm, and the reaction times is 1-6h, and the selectivity of diphenylene-oxide is 89%.
In the patent of US 4065469A, adopting 2-cyclohexenyl hexamethylene ketone is raw material, being catalyzer on the different carrier of different oxidation thing load; In lower pressure and higher temperature; With the air is oxygenant, under the condition of inertia dilution reagent on fixed bed the synthetic diphenylene-oxide of oxidation continuously, its catalyzer is the metal oxide supported on carriers such as silicon-dioxide, aluminum oxide and zeyssatite of III A, IV A, V A, VI A and VII A family; Reaction pressure is 0-10atm; Temperature of reaction is 400-550 ℃, and the mol ratio of air and 2-cyclohexenyl hexamethylene ketone is 8-30:1, and inertia dilution reagent is water vapour, nitrogen and saturated alkane etc.; The mol ratio of inertia reagent and 2-cyclohexenyl hexamethylene ketone is 10-70:1; The residence time of 2-cyclohexenyl hexamethylene ketone on catalyzer is 0.2-2.5s, and the transformation efficiency of 2-cyclohexenyl hexamethylene ketone is 77.5%, and the selectivity of diphenylene-oxide is 80%.
In the patent of US 4490550A, adopt, consist of catalyzer with in the metals such as the carboxylate salt of palladium and antimony, tin, cobalt, lead, zinc, manganese, potassium, chromium one or more with hexane or heptane solvent as the solid material phenyl ether; At lower pressure and temperature, with the air be under the oxygenant condition in reaction kettle the synthetic diphenylene-oxide of oxidation step, the carboxylate salt of its palladium is the carboxylate salt of 2-4 carbon; The charge capacity of palladium and the mol ratio of other metals are 1:0.2-50; Reaction pressure is 0-10atm, and temperature of reaction is 120-200 ℃, and the reaction times is 0.03-10h; The transformation efficiency of phenyl ether is 97%, and the selectivity of diphenylene-oxide is 95%.
Main in the compound method of diphenylene-oxide at present is raw material oxidation synthetic under higher pressure and temperature with phenyl ether or 2-cyclohexenyl hexamethylene ketone, but this method is big for the suitability for industrialized production energy consumption, is unfavorable for the control of production cost.2,4,8-trichlorine diphenylene-oxide is a kind of by product in the triclosan production process, Wei dioxin a kind of, traditional treatment method is for burning contaminate environment.With 2,4, the technology that 8-trichlorine diphenylene-oxide hydrodechlorination prepares diphenylene-oxide is that pollutent is utilized again, and can bring the high product added value.So exploitation is with 2,4, the technology that 8-trichlorine diphenylene-oxide hydrodechlorination prepares diphenylene-oxide has bigger economic benefit and high social, and large-scale industrialization production diphenylene-oxide is had significance.
Summary of the invention
The object of the present invention is to provide a kind of at tank reactor, under normal pressure and lower temperature conditions, 2,4,8-trichlorine diphenylene-oxide catalytic hydrogenation and dechlorination prepares the method for diphenylene-oxide.
Technical scheme of the present invention is: a kind of method for preparing diphenylene-oxide, and its concrete steps are following: with 2,4; 8-trichlorine diphenylene-oxide adds catalyzer, phase-transfer catalyst as reaction raw materials, and aromatic hydrocarbon is as solvent; Add alkaline solution again; And feeding hydrogen, under 40 ~ 100 ℃ of conditions, react 0.5 ~ 6h, obtain diphenylene-oxide through separating.
Preferred described phase-transfer catalyst is benzyltriethylammoinium chloride, tetrabutylammonium chloride or tri-n-octyl methyl ammonium chloride, phase-transfer catalyst and 2,4 wherein, and the mass ratio of 8-trichlorine diphenylene-oxide is 1: (5 ~ 15); Preferred described solvent is toluene, p-Xylol or ethylbenzene, solvent and 2,4 wherein, and the mass ratio of 8-trichlorine diphenylene-oxide is 5 ~ 15: 1; Preferred described alkaline solution is the aqueous solution of sodium hydroxide or Pottasium Hydroxide; The massfraction of sodium hydroxide or Pottasium Hydroxide is 5 ~ 15% in the alkaline solution; Alkaline solution and 2,4, the mass ratio of 8-trichlorine diphenylene-oxide is 5 ~ 10: 1.It is 10 ~ 100mL/min that preferred hydrogen feeds speed.
Preferred described catalyzer is a noble metal carrier catalyst, and wherein carrier is gac or zeyssatite, and precious metal is Pd or Pt; Wherein the load quality of precious metal is 1 ~ 10% of a support of the catalyst quality; Described catalyzer and 2,4, the mass ratio of 8-trichlorine diphenylene-oxide is 1: 5 ~ 15.
Catalyzer of the present invention can make with ordinary method, also can preferred following method make, and its concrete steps are following:
(1) preparation of catalyst precursor: support of the catalyst is dry for standby after the anchoring treatment of pickling, alkali cleaning, oxide treatment and nitrite; Mixing solutions with the muriate and the alkali-metal nitrite of precious metal is dissolved in hydrochloric acid and methyl alcohol is added drop-wise on the support of the catalyst, and dipping 8 ~ 16h obtains the precursor solution of catalyzer; Wherein said support of the catalyst is gac or zeyssatite, and described precious metal chloride is PdCl
2Perhaps PtCl
2The dripping quantity of described mixing solutions is that the quality that loads to the precious metal on the carrier accounts for 1 ~ 10% of support of the catalyst quality;
(2) pre-treatment of catalyzer precursor: under 50 ~ 100 ℃ of conditions, formaldehyde and Hydrazine Hydrate 80 mixing solutions joined reduce 3 ~ 6h in the complex catalyst precursor liquid solution that step (1) makes, through filter, washing, dry, cooling, obtain catalyzer.
Preferred above-mentioned alkali-metal nitrite is Sodium Nitrite or potassium nitrite; The muriate of precious metal and alkali-metal nitrite mol ratio are 1: 1 ~ 10.
The mixing solutions of hydrochloric acid described in the preferred steps 1 and methyl alcohol is that the hydrochloric acid and methyl alcohol 1: 1 by volume ~ 5 mixing of massfraction 1 ~ 10% get; The add-on of mixing solutions can be dissolved solute and got final product.The mixing solutions of formaldehyde described in the preferred steps 2 and Hydrazine Hydrate 80 is that the formaldehyde of massfraction 10 ~ 37% and the Hydrazine Hydrate 80 of massfraction 50 ~ 80% are that 10 ~ 20: 1 mixing gets by volume.
In the above-mentioned compound method, 2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide reaches 99.96%, and the yield of diphenylene-oxide is up to 99.57%.
Beneficial effect:
The present invention adopts noble metal carrier catalyst, under normal pressure and lesser temps (being lower than 100 ℃) condition with 2,4; 8-trichlorine diphenylene-oxide is the synthetic diphenylene-oxide of raw material hydrodechlorination, 2,4; The transformation efficiency of 8-trichlorine diphenylene-oxide and the yield of diphenylene-oxide are all than higher (2; 4, the transformation efficiency of 8-trichlorine diphenylene-oxide reaches 99.96%, and the yield of diphenylene-oxide is up to 99.57%.), be applicable to the suitability for industrialized production diphenylene-oxide.
Embodiment
Embodiment 1
Take by weighing a certain amount of active carbon powder its anchoring treatment through pickling, alkali cleaning, oxide treatment and Sodium Nitrite is obtained support of the catalyst, the oven dry back is subsequent use.
Take by weighing 0.4422g purity and be 59.5% Palladous chloride and 1.0239g Sodium Nitrite; And it fully is added drop-wise in the aqueous solution of 3g support of the catalyst after the dissolving in 1% Hydrogen chloride and 1: 1 by volume 50mL mixing solutions of methyl alcohol; Dipping 8h; The Hydrazine Hydrate 80 that adds 10mL37% formaldehyde and 1mL80% reduces 6h under 50 ℃ of conditions, cooled and filtered, washing, drying and cool off obtain charge capacity and be 5% Pd/C catalyzer.
In tank reactor, pack into the Pd/C catalyzer of 0.5g 5%, 1.0g tri-n-octyl methyl ammonium chloride, 5.0g2; 4,8-trichlorine diphenylene-oxide, 30mL toluene and 15%NaOH aqueous solution 25mL; Hydrogen feeds speed 100mL/min; Normal pressure reacts 6.0h under 100 ℃ of conditions, makes diphenylene-oxide through conventional the separation.2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide is 94.71%, and the yield of diphenylene-oxide is 91.12%
Embodiment 2
Take by weighing a certain amount of zeyssatite its anchoring treatment through pickling, alkali cleaning, oxide treatment and potassium nitrite is obtained support of the catalyst, the oven dry back is subsequent use.
Take by weighing 0.9336g purity and be 59.5% Palladous chloride and 0.2663g potassium nitrite; And it fully is added drop-wise in the aqueous solution of 3g support of the catalyst after the dissolving in 3% Hydrogen chloride and 1: 5 by volume 50mL mixing solutions of methyl alcohol; Dipping 12h; The Hydrazine Hydrate 80 that adds 20mL27% formaldehyde and 1mL50% reduces 3h under 100 ℃ of conditions, cooled and filtered, washing, drying and cool off obtain charge capacity and be 10% Pd/ zeyssatite catalyzer.
In tank reactor, pack into the Pd/ zeyssatite catalyzer of 1.0g 10%, the 0.35g benzyltriethylammoinium chloride, 5.0g 2; 4; 8-trichlorine diphenylene-oxide 85mL p-Xylol and 10%KOH aqueous solution 50mL, hydrogen feeds speed 70mL/min, normal pressure; React 0.5h under 80 ℃ of conditions, make diphenylene-oxide through conventional the separation.2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide is 95.49%, and the yield of diphenylene-oxide is 93.07%
Embodiment 3
Take by weighing a certain amount of diatomite powder its anchoring treatment through pickling, alkali cleaning, oxide treatment and potassium nitrite is obtained support of the catalyst, the oven dry back is subsequent use.
Take by weighing 0.0695g purity and be 59.5% platinum chloride and 0.0660g potassium nitrite; And it fully is added drop-wise in the aqueous solution of 3g support of the catalyst after the dissolving in 5% Hydrogen chloride and 1: 3 by volume 50mL mixing solutions of methyl alcohol; Dipping 16h; The Hydrazine Hydrate 80 that adds 15mL10% formaldehyde and 1mL60% reduces 6h under 75 ℃ of conditions, cooled and filtered, washing, drying and cool off obtain charge capacity and be 1% Pt/ zeyssatite catalyzer.
In tank reactor, pack into the Pt/ zeyssatite catalyzer of 0.35g 1%, 0.6g tetrabutylammonium chloride, 5g2; 4; 8-trichlorine diphenylene-oxide 50mL ethylbenzene and 5%NaOH aqueous solution 40mL, hydrogen feeds speed 10mL/min, normal pressure; React 6.0h under 40 ℃ of conditions, make diphenylene-oxide through conventional the separation.2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide is 90.98%, and the yield of diphenylene-oxide is 83.19%
Embodiment 4
Take by weighing a certain amount of active carbon powder its anchoring treatment through pickling, alkali cleaning, oxide treatment and Sodium Nitrite is obtained support of the catalyst, the oven dry back is subsequent use.
Take by weighing 0.7306g purity and be 59.5% Palladous chloride and 1.0239g Sodium Nitrite; And it fully is added drop-wise in the aqueous solution of 3g support of the catalyst after the dissolving in 7% Hydrogen chloride and 1: 2 by volume 50mL mixing solutions of methyl alcohol; Dipping 10h; The Hydrazine Hydrate 80 that adds 10mL37% formaldehyde and 1mL50% reduces 4h under 80 ℃ of conditions, cooled and filtered, washing, drying and cool off obtain charge capacity and be 8% Pd/C catalyzer.
In tank reactor, pack into the Pd/C catalyzer of 0.7g 8%, 0.6g tri-n-octyl methyl ammonium chloride, 5g2; 4; 8-trichlorine diphenylene-oxide 60mL p-Xylol and 15%NaOH aqueous solution 25mL, hydrogen feeds speed 60mL/min, normal pressure; React 2.0h under 75 ℃ of conditions, make diphenylene-oxide through conventional the separation.2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide is 98.71%, and the yield of diphenylene-oxide is 95.22%
Embodiment 5
Take by weighing a certain amount of diatomite powder its anchoring treatment through pickling, alkali cleaning, oxide treatment and Sodium Nitrite is obtained support of the catalyst, the oven dry back is subsequent use.
Take by weighing 0.3619g purity and be 59.5% platinum chloride and 0.5120g Sodium Nitrite; And it fully is added drop-wise in the aqueous solution of 3g support of the catalyst after the dissolving in the 50mL mixing solutions of 1:4 at 10% Hydrogen chloride and methyl alcohol by volume; Dipping 14h; The Hydrazine Hydrate 80 that adds 13mL20% formaldehyde and 1mL70% reduces 5h under 60 ℃ of conditions, cooled and filtered, washing, drying and cool off obtain charge capacity and be 5% Pt/ zeyssatite catalyzer.
In tank reactor, pack into the Pt/ zeyssatite catalyzer of 0.5g 5%, the 0.7g benzyltriethylammoinium chloride, 5g 2; 4; 8-trichlorine diphenylene-oxide 40mL ethylbenzene and 5%KOH aqueous solution 30mL, hydrogen feeds speed 80mL/min, normal pressure; React 3.0h under 60 ℃ of conditions, make diphenylene-oxide through conventional the separation.2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide is 92.68%, and the yield of diphenylene-oxide is 81.95%
Embodiment 6
Take by weighing a certain amount of active carbon powder its anchoring treatment through pickling, alkali cleaning, oxide treatment and Sodium Nitrite is obtained support of the catalyst, the oven dry back is subsequent use.
Take by weighing 0.8310g purity and be 59.5% Palladous chloride and 0.2048g Sodium Nitrite; And it fully is added drop-wise in the aqueous solution of 3g support of the catalyst after the dissolving in 8% Hydrogen chloride and 1: 1 by volume 50mL mixing solutions of methyl alcohol; Dipping 16h; The Hydrazine Hydrate 80 that adds 10mL37% formaldehyde and 1mL50% reduces 3h under 70 ℃ of conditions, cooled and filtered, washing, drying and cool off obtain charge capacity and be 9% Pd/C catalyzer.
In tank reactor, pack into the Pd/C catalyzer of 0.7g 9%, the 0.5g tetrabutylammonium chloride, 5g 2; 4,8-trichlorine diphenylene-oxide 70mL toluene and 10%NaOH aqueous solution 20mL, hydrogen feeds speed 70mL/min; Normal pressure reacts 1.0h under 80 ℃ of conditions, makes diphenylene-oxide through conventional the separation.2,4, the transformation efficiency of 8-trichlorine diphenylene-oxide is 99.31%, and the yield of diphenylene-oxide is 98.72%.
Claims (8)
1. method for preparing diphenylene-oxide, its concrete steps are following: with 2,4; 8-trichlorine diphenylene-oxide adds catalyzer, phase-transfer catalyst as reaction raw materials, and aromatic hydrocarbon is as solvent; Add alkaline solution again; And feeding hydrogen, under 40 ~ 100 ℃ of conditions, react 0.5 ~ 6h, obtain diphenylene-oxide through separating.
2. method according to claim 1; It is characterized in that described phase-transfer catalyst is benzyltriethylammoinium chloride, tetrabutylammonium chloride or tri-n-octyl methyl ammonium chloride; Phase-transfer catalyst and 2,4 wherein, the mass ratio of 8-trichlorine diphenylene-oxide is 1: (5 ~ 15); Described solvent is toluene, p-Xylol or ethylbenzene, solvent and 2,4 wherein, and the mass ratio of 8-trichlorine diphenylene-oxide is 5 ~ 15: 1; Described alkaline solution is the aqueous solution of sodium hydroxide or Pottasium Hydroxide; The massfraction of sodium hydroxide or Pottasium Hydroxide is 5 ~ 15% in the alkaline solution; Alkaline solution and 2,4, the mass ratio of 8-trichlorine diphenylene-oxide is 5 ~ 10: 1.
3. method according to claim 1 is characterized in that it is 10 ~ 100mL/min that hydrogen feeds speed.
4. method according to claim 1 is characterized in that, described catalyzer is a noble metal carrier catalyst, and wherein carrier is gac or zeyssatite, and precious metal is Pd or Pt; Wherein the load quality of precious metal is 1 ~ 10% of a support of the catalyst quality; Described catalyzer and 2,4, the mass ratio of 8-trichlorine diphenylene-oxide is 1: 5 ~ 15.
5. method according to claim 1 is characterized in that described catalyzer is made by following method, and its concrete steps are following:
(1) preparation of catalyst precursor: support of the catalyst is dry for standby after the anchoring treatment of pickling, alkali cleaning, oxide treatment and nitrite; Mixing solutions with the muriate and the alkali-metal nitrite of precious metal is dissolved in hydrochloric acid and methyl alcohol is added drop-wise on the support of the catalyst, and dipping 8 ~ 16h obtains the precursor solution of catalyzer; Wherein said support of the catalyst is gac or zeyssatite, and described precious metal chloride is PdCl
2Perhaps PtCl
2The dripping quantity of described mixing solutions is that the quality that loads to the precious metal on the carrier accounts for 1 ~ 10% of support of the catalyst quality;
(2) pre-treatment of catalyzer precursor: under 50 ~ 100 ℃ of conditions, formaldehyde and Hydrazine Hydrate 80 mixing solutions joined reduce 3 ~ 6h in the complex catalyst precursor liquid solution that step (1) makes, through filter, washing, dry, cooling, obtain catalyzer.
6. method according to claim 5 is characterized in that described alkali-metal nitrite is Sodium Nitrite or potassium nitrite; The muriate of precious metal and alkali-metal nitrite mol ratio are 1: 1 ~ 10.
7. method according to claim 5, the mixing solutions that it is characterized in that hydrochloric acid described in the step 1 and methyl alcohol are that the hydrochloric acid and methyl alcohol 1: 1 by volume ~ 5 mixing of massfraction 1 ~ 10% get.
8. method according to claim 5, the mixing solutions that it is characterized in that formaldehyde described in the step 2 and Hydrazine Hydrate 80 are that the formaldehyde of massfraction 10 ~ 37% and the Hydrazine Hydrate 80 of massfraction 50 ~ 80% are that 10 ~ 20: 1 mixing gets by volume.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755689A (en) * | 2013-12-25 | 2014-04-30 | 连云港恒运医药科技有限公司 | Preparation method for prucalopride degradation impurities |
| CN106669667A (en) * | 2015-11-05 | 2017-05-17 | 中国石油化工股份有限公司大连石油化工研究院 | Preparation method for dehydrogenation catalyst |
| CN112973763A (en) * | 2021-03-03 | 2021-06-18 | 太原理工大学 | Dibenzofurans hydrodeoxygenation catalyst and preparation method and application thereof |
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| Title |
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| E.V. GOLUBINA等: "The role of Fe addition on the activity of Pd-containing catalysts in multiphase hydrodechlorination", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755689A (en) * | 2013-12-25 | 2014-04-30 | 连云港恒运医药科技有限公司 | Preparation method for prucalopride degradation impurities |
| CN103755689B (en) * | 2013-12-25 | 2016-06-29 | 连云港恒运医药科技有限公司 | The preparation method of prucalopride degradation impurity |
| CN106669667A (en) * | 2015-11-05 | 2017-05-17 | 中国石油化工股份有限公司大连石油化工研究院 | Preparation method for dehydrogenation catalyst |
| CN106669667B (en) * | 2015-11-05 | 2019-01-08 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of preparation method of dehydrogenation |
| CN112973763A (en) * | 2021-03-03 | 2021-06-18 | 太原理工大学 | Dibenzofurans hydrodeoxygenation catalyst and preparation method and application thereof |
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