CN114805032A - Method for preparing o-phenylphenol by reducing dibenzofuran - Google Patents
Method for preparing o-phenylphenol by reducing dibenzofuran Download PDFInfo
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- dibenzofuran
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- soluble
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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 296
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 235000010292 orthophenyl phenol Nutrition 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 64
- 238000011068 loading method Methods 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 238000009495 sugar coating Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000003518 caustics Substances 0.000 claims description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 24
- 238000005265 energy consumption Methods 0.000 abstract description 14
- 239000004306 orthophenyl phenol Substances 0.000 description 66
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 59
- 238000000605 extraction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 32
- 239000000395 magnesium oxide Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000003513 alkali Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- FLSGOMWWJAPWFM-UHFFFAOYSA-N dibenzofuran toluene Chemical compound C1(=CC=CC=C1)C.C1=CC=CC=2OC3=C(C21)C=CC=C3 FLSGOMWWJAPWFM-UHFFFAOYSA-N 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07C37/01—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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing o-phenylphenol, which comprises the step of carrying out hydrogenation reaction on dibenzofuran in the presence of a catalyst, wherein the catalyst comprises a carrier and an active component with a catalytic effect, and the carrier comprises alpha-Al 2 O 3 And MgO, the active component including one or more of platinum element, palladium element and rhodium element. The method can use high-concentration dibenzofuran as a raw material, and realizes that the conversion rate of dibenzofuran reaction and the selectivity of o-phenylphenol are not reduced while the energy consumption is greatly reduced. The catalyst used in the method can stably run for more than 4000 hours, has industrial conditions and high economic value.
Description
Technical Field
The invention belongs to the field of preparation of o-phenylphenol, and particularly relates to a method for preparing o-phenylphenol by reducing dibenzofuran.
Background
Ortho-phenylphenol (OPP) is a widely used fine chemical. In recent years, a novel OPP production method, namely a dibenzofuran reduction method is reported, and although no industrial production practice exists at present, the method has a wide application prospect. The dibenzofuran is an important component in the wash oil and accounts for about 5-10% of the mass of the wash oil. The washing oil comes from the 230-300 ℃ distillation section of the coal tar and accounts for about 4.5-10% of the mass of the coal tar. China is rich in coal resources, the supply amount of washing oil is large, and the space for producing OPP by using dibenzofuran as a raw material is large.
CN108947775A discloses a dibenzofuran hydrogenation process using a reactive distillation column, wherein the catalyst used is a copper-loaded catalyst of a nano titanium oxide mesoporous composite material; the concentration of the used dibenzofuran raw material is less than 17%.
CN106495991A discloses a hydrofining reaction tower for carrying out a dibenzofuran reduction process, a supported CoMo catalyst is used, and a carrier is SiO 2 、Al 2 O 3 、TiO 2 、SiO 2 -Al 2 O 3 Or Al 2 O 3 -TiO 2 (ii) a The concentration of the used dibenzofuran raw material is less than 20%.
The processes all use solvents, and have the defects of low concentration of dibenzofuran, high energy consumption, high investment, short service life of the catalyst and poor economical efficiency, thus affecting the industrial prospect. In the prior art, acid and alkali treatment is commonly used for separating OPP products, but the used technology has low separation efficiency and large waste water generation amount.
Therefore, there is a need in the art for a method for preparing OPP by means of dibenzofuran reduction that can use high concentrations of dibenzofuran as a starting material, with long catalyst life, and with high OPP selectivity and yield.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing o-phenylphenol by reducing dibenzofuran. The method of the invention realizes high dibenzofuran conversion rate and high OPP selectivity, and when high-concentration dibenzofuran is used as a raw material, the dibenzofuran conversion rate and the OPP selectivity can still be kept at high levels, the production energy consumption is greatly reduced, and the catalyst can stably run for more than 4000 hours for a long time. The invention further provides a method for separating products by using multistage extraction, which greatly reduces the production amount of waste water and improves the yield and purity of products. The method of the invention is suitable for industrial production and has high economic value.
Specifically, the invention provides a method for preparing o-phenylphenol, which comprises the step of subjecting dibenzofuran to hydrogenation reaction in the presence of a catalyst, wherein the catalyst comprises a carrier and a catalytically active component, and the carrier comprises alpha-Al 2 O 3 And MgO, the active component including one or more of platinum element, palladium element and rhodium element.
In one or more embodiments, the hydrogenation reaction is carried out in a fixed bed reactor.
In one or more embodiments, the dibenzofuran starting material used in the process is pure dibenzofuran or a dibenzofuran solution having a dibenzofuran mass fraction > 35%, preferably a dibenzofuran mass fraction of 50% to 70%, the dibenzofuran solution solvent preferably being selected from alkanes containing 4 to 9 carbon atoms and aromatic hydrocarbons containing 6 to 9 carbon atoms, more preferably from one or more of hexane, cyclohexane, benzene, toluene and xylene.
In one or more embodiments, the mass space velocity of the dibenzofuran in the hydrogenation reaction is 0.4h -1 -2h -1 Preferably 0.7h -1 -1.5h -1 。
In one or more embodiments, the hydrogenation reaction has a ratio of mass of hydrogen to mass of dibenzofuran of greater than 0.12: 1, preferably (0.3-2): 1.
in one or more embodiments, the preheating temperature for the hydrogenation reaction is from 250 ℃ to 450 ℃, preferably from 350 ℃ to 400 ℃.
In one or more embodiments, the reaction temperature of the hydrogenation reaction is from 300 ℃ to 450 ℃, preferably from 350 ℃ to 420 ℃.
In one or more embodiments, the reaction pressure of the hydrogenation reaction is from 0.5MPa to 2MPa, preferably from 0.7MPa to 1.5 MPa.
In one or more embodiments, the active component is elemental platinum.
In one or more embodiments, the support comprises, alpha-Al 2 O 3 The mass of the MgO accounts for 70-96% of the total mass of the carrier, and the mass of the MgO accounts for 4-30% of the total mass of the carrier; preferably, in the carrier, α -Al 2 O 3 The mass of the MgO accounts for 76-95% of the total mass of the carrier, and the mass of the MgO accounts for 5-24% of the total mass of the carrier.
In one or more embodiments, the mass of the active component in the catalyst is between 0.1% and 20%, preferably between 0.2% and 10% of the mass of the support.
In one or more embodiments, the catalyst wherein the MgO is located in the alpha-Al 2 O 3 Of (2) is provided.
In one or more embodiments, the catalyst is prepared by a process comprising the steps of:
(1) loading soluble magnesium-containing compound on alpha-Al 2 O 3 Surface, calcining to obtain a carrier;
(2) loading a soluble compound containing an active component on the surface of the carrier to obtain a catalyst precursor;
(3) and calcining the catalyst precursor.
In one or more embodiments, the method of preparing a catalyst has one or more of the following features:
the soluble magnesium-containing compound is selected from one or more of magnesium nitrate, magnesium acetate and magnesium chloride;
in the step (1), a sugar-coating machine, a ball rolling machine or a rotary mixer is used for carrying out the loading, and the rotating speed of the sugar-coating machine, the ball rolling machine or the rotary mixer is preferably 5-40 rpm;
in the step (1), soluble magnesium-containing compound is loaded on alpha-Al by adopting a spraying or dipping mode 2 O 3 A surface;
the calcining mode in the step (1) is as follows: heating the mixture from room temperature to 500-700 ℃ at a heating rate of 3-10 ℃/min, and then roasting for 2-8 h;
in the step (1), before calcination, alpha-Al loaded with soluble magnesium-containing compound is subjected to calcination 2 O 3 Drying, wherein the drying is preferably carried out for 5-16 h at the temperature of 60-120 ℃;
the soluble compound containing the active component is selected from one or more of a soluble platinum-containing compound, a soluble palladium-containing compound and a soluble rhodium-containing compound, and the soluble platinum-containing compound is selected from one or more of chloroplatinic acid, tetraammineplatinum nitrate and tetraammineplatinum chloride;
in the step (2), a sugar-coating machine, a ball rolling machine or a rotary mixer is used for carrying out the loading, and the rotating speed of the sugar-coating machine, the ball rolling machine or the rotary mixer is preferably 5-40 rpm;
in the step (2), soluble compounds containing active components are loaded on the surface of the carrier in a spraying or dipping mode;
the step (2) also comprises the step of drying the carrier loaded with the soluble compound containing the active component, wherein the drying is preferably carried out for 5-16 h at the temperature of 60-120 ℃;
the calcining mode in the step (3) is as follows: heating the mixture from room temperature to 500-700 ℃ at a heating rate of 3-10 ℃/min, and then roasting for 2-8 h.
In one or more embodiments, the method of preparing the catalyst further comprises the steps of:
(4) and (4) reducing the catalyst obtained in the step (3) for 2-6 h at the temperature of 350-450 ℃.
In one or more embodiments, the process further comprises subjecting the product solution of the hydrogenation reaction to multiple stages of caustic washing, wherein fresh caustic is mixed with the organic phase subjected to the last stage of caustic washing, and then the caustic wash is mixed in reverse order with the organic phase subjected to each stage of caustic washing.
In one or more embodiments, the ratio of the mass of the lye to the mass of the product solution is (0.1-3): 1.
drawings
FIG. 1 is an XRD spectrum of the catalyst obtained in preparation example 1 of the present invention.
FIG. 2 is a schematic diagram of the process for preparing o-phenylphenol by the reduction of dibenzofuran in examples 1-5 of the present invention.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The terms "comprising," including, "" containing, "and the like, herein, encompass the meanings of" consisting essentially of … … "and" consisting of … …, "e.g., when" A comprises B and C, "A consists of B and C" is disclosed herein is to be considered disclosed herein.
All features defined herein as numerical ranges or percentage ranges, such as numbers, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, when embodiments or examples are described, it is to be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The o-phenylphenol (OPP) is a fine chemical with wide application, and the preparation of the OPP by the reduction of the dibenzofuran has wide prospect in China. The existing method for preparing OPP by reducing dibenzofuran has the problems of low OPP selectivity, high catalyst cost, short service life and the like. The existing method for preparing OPP by reducing dibenzofuran generally uses low-concentration dibenzofuran solution as dibenzofuran raw material, and has large energy consumption and high investment. The existing method for preparing OPP by reducing dibenzofuran has the disadvantages of low separation efficiency of product separation technology and high waste water generation amount.
The method for preparing o-phenylphenol comprises the step of subjecting dibenzofuran to hydrogenation reaction in the presence of a catalyst, wherein the catalyst comprises a carrier and an active component, and the carrier comprises alpha-Al 2 O 3 And MgO, the active component including one or more of platinum element, palladium element and rhodium element.
In the present invention, the support has the meaning conventional in the art and is a support for the active component in the catalyst. The invention uses alumina with specific crystal form-alpha-Al 2 O 3 As carrier core, in alpha-Al 2 O 3 The surface is coated with alkaline oxide to form an alkaline composite carrier with low specific surface area, and then the active metal is loaded on the composite carrier, the carrier with low specific surface area is beneficial to dispersing more active metal on the surface of the carrier, thereby not only improving the utilization efficiency of noble metal and reducing the loading capacity of noble metal components, but also being beneficial to the diffusion of reaction products, improving the OPP selectivity and reducing the cost of the catalyst, and the catalyst used by the invention has good stability and can be stableThe constant operation is over 4000 h. The catalyst used in the invention can still keep high dibenzofuran conversion rate and OPP selectivity when catalyzing high-concentration dibenzofuran raw materials, so that the solvent dosage can be greatly reduced, and the energy consumption is greatly reduced.
alpha-Al contained in the catalyst used in the present invention 2 O 3 Preferably, the alpha-Al particles have a particle size of 2 to 5mm, for example, 2 to 4mm, 3. + -. 0.5mm 2 O 3 . It is understood that when the particles are not spherical, the particle size (also referred to as diameter) as described herein refers to the equivalent particle size of the particles. alpha-Al 2 O 3 The shape of the particles may be a stripe, sphere, hollow type, etc. In some embodiments, the catalyst used in the present invention comprises alpha-Al 2 O 3 Is 3 +/-0.5 mm strip-shaped alpha-Al 2 O 3 . The catalyst used in the invention also comprises MgO, and the MgO exists in alpha-Al 2 O 3 Of (2) is provided. The carrier of the catalyst used in the invention is MgO/alpha-Al 2 O 3 The composite oxide has the characteristics of alkalinity and low specific surface area. The carrier of the catalyst used in the invention adopts the formed inert alpha-Al 2 O 3 The material (commonly known as corundum) has the characteristics of high strength, good stability, inertia, low specific surface area and the like. The carrier of the catalyst used in the invention is beneficial to dispersing more active metals on the outer surface of the carrier, and the dosage of noble metals is reduced; the diffusion of reaction products is facilitated, and the OPP selectivity is improved; the alkalinity of the catalyst is also beneficial to reducing the generation of byproducts and improving the OPP selectivity.
In the catalyst used in the present invention, α -Al 2 O 3 And the total mass of MgO may be more than 90%, more than 95%, more than 98%, more than 99% or 100% of the total mass of the carrier. alpha-Al 2 O 3 The mass of (b) may be 70% to 96%, preferably 76% to 95%, for example 78%, 92%, 84 ± 5%, 84 ± 2% or 84 ± 1% of the total mass of the carrier. The amount of MgO may be from 4% to 30%, preferably from 5% to 24%, for example 8%, 12%, 16. + -. 5%, 16. + -. 2% or 16. + -. 1% by mass of the total mass of the support. The invention finds use with alpha-Al 2 O 3 And a carrier having a MgO content within the aforementioned range, is advantageousThe conversion rate of hydrogenation reaction is obviously improved while high OPP selectivity is kept.
The active component of the catalyst used in the invention is selected from one or more of platinum element, palladium element and rhodium element, and is preferably platinum element. In the present invention, the active component has the meaning conventional in the art and is a catalytically active species in the catalyst. The catalysts used according to the invention are obtained by calcination and optionally further reduction (also called activation) of the support loaded with soluble compounds containing the active component. The soluble active component-containing compound described herein is selected from one or more of a soluble platinum-containing compound, a soluble palladium-containing compound, and a soluble rhodium-containing compound. In some embodiments, the soluble compound comprising an active component is a soluble platinum-containing compound. It will be appreciated that the active component in the unreduced catalyst is generally present in the form of a metal oxide (platinum oxide, palladium oxide and/or rhodium oxide). The active component platinum in the reduced catalyst is usually present in the form of elemental metal (platinum, palladium and/or rhodium) or a mixture of elemental metal and metal oxide (platinum oxide, platinum oxide and/or rhodium oxide), the ratio of metal oxide to elemental metal being dependent on the degree of reduction.
The catalyst used in the invention ensures good dibenzofuran conversion rate and OPP selectivity, and simultaneously, the content of the required active component (such as platinum element) is obviously reduced compared with other catalysts. In the catalyst used in the present invention, the mass of the active component (e.g., platinum element) may be 0.1% to 20%, e.g., 0.2% to 10%, of the mass of the carrier. Herein, unless otherwise specified, the mass or content of the active component is calculated as the mass of the active metal element. In preferred embodiments, the mass of the active component (e.g., platinum element) does not exceed 10%, 5%, 2%, 1%, 0.6%, or even 0.5% of the mass of the support. In some preferred embodiments, the mass of the active component (e.g., platinum element) is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 5%, 10% or within the range of any two of these values of the mass of the support. Herein, the mass ratio of the active component to the carrier is also referred to as the active component loading amount.
The catalysts used according to the invention may optionally contain small amounts of auxiliaries to improve the catalytic performance. The auxiliary agent suitable for the catalyst used in the present invention may be an auxiliary agent conventionally added to the catalyst, and for example, a compound of potassium, sodium, calcium or the like may be selected as the auxiliary agent as needed.
In some preferred embodiments, the catalyst used in the present invention comprises α -Al 2 O 3 MgO, and one selected from the group consisting of an oxide of the active component, a simple substance of the active component, and a mixture of a simple substance of the active component and an oxide of the active component, or from alpha-Al 2 O 3 MgO, and one selected from the group consisting of an oxide of an active component, a simple substance of an active component, and a mixture of a simple substance of an active component and an oxide of an active component, wherein the active component is preferably platinum element; preferably, in the catalyst, α -Al 2 O 3 The mass of (A) is 76-84%, preferably 76-95%, such as 84 + -5%, 84 + -2% or 84 + -1%, the mass of MgO is 16-24%, preferably 5-24%, such as 16 + -5%, 16 + -2% or 16 + -2%, and the mass of active component is 0.1-20%, preferably 0.2-10%, such as 0.1-1%, 0.2-1%, 0.5 + -0.2% or 0.5 + -0.1% of the total mass of the carrier.
The catalyst used in the present invention can be prepared by a process comprising the steps of:
(1) loading soluble magnesium-containing compound on alpha-Al 2 O 3 Surface, calcining to obtain a carrier;
(2) loading a soluble compound containing an active component on the surface of the carrier to obtain a catalyst precursor;
(3) and calcining the catalyst precursor.
The soluble magnesium-containing compound suitable for use in the present invention may be a soluble magnesium salt, such as one or more of magnesium nitrate, magnesium acetate and magnesium chloride. The soluble magnesium-containing compound can be prepared into an aqueous solution to lead the alpha-Al to be 2 O 3 Contacting with an aqueous solution of a soluble magnesium-containing compound to render the compound solubleMagnesium-containing compound supported on alpha-Al 2 O 3 A surface. The concentration of the aqueous solution of the soluble magnesium-containing compound (e.g. aqueous magnesium nitrate) may be 20-40 wt%, for example 32 ± 2 wt%. The alpha-Al can be sprayed or dipped 2 O 3 Contacting with an aqueous solution of a soluble magnesium-containing compound. Spraying or dipping may be carried out under heat (e.g., 20-70 deg.C) to promote alpha-Al 2 O 3 For the adsorption of the aqueous solution of the magnesium-containing compound and allows some drying to occur during the contacting. For example, spraying may be accompanied by forced air drying, the temperature of the forced air may be 20-70 deg.C, for example 50 + -10 deg.C. The blowing is mainly to dry the material to a certain extent while loading so as to enable the alpha-Al 2 O 3 The effect of absorbing the magnesium-containing compound aqueous solution is better. After loading by immersion, the mixture can be stirred and evaporated to dryness at 80 +/-20 ℃. In some embodiments, the loading operation (e.g., spray plus forced air drying) of step (1) is performed in a sugar coater, a ball roller, or a rotary compounder. The rotating speed of the sugar-coating machine, the ball rolling machine or the rotary mixer is preferably 5-40 rpm. The use of sugar coating machines, ball rollers or rotary blenders for loading is beneficial to industrial scale-up. The rotating speed is set to be 5-40 rpm, so that the materials can be rolled in the machine, the purpose of fully and uniformly loading is achieved, and meanwhile, material abrasion caused by too fast speed is avoided.
Loading soluble magnesium-containing compound on alpha-Al 2 O 3 After the surface treatment, the carrier can be obtained by drying and then calcining. For alpha-Al loaded with soluble magnesium-containing compound 2 O 3 The drying may be carried out at 60 to 120 ℃, for example, 100 + -10 ℃ for 5 to 16 hours, for example, 5 to 6 hours.
In the invention, for the alpha-Al loaded with soluble magnesium-containing compound 2 O 3 The calcination was carried out in the following manner: heating the mixture from room temperature to 500-700 deg.C, for example 600 + -50 deg.C, at a heating rate of 3-10 deg.C/min, for example 5 + -1 deg.C/min, and then calcining the mixture at the heated temperature for 2-8 h, for example 5 + -1 h. The invention controls the heating rate to be 3-10 ℃/min, and can prevent the loaded components from evaporating or decomposing too fast in the roasting processAffecting the uniformity of the final load; meanwhile, the roasting time and energy consumption are prevented from being increased due to too slow temperature rise. According to the invention, the roasting constant temperature is controlled to be 500-700 ℃, the time is controlled to be 2-8 h, and the load components can be fully decomposed within the shortest time of minimum energy consumption.
In the present invention, the operation of step (1) may be performed only once or repeatedly for several times during the preparation of the carrier, i.e., MgO may be coated on α -Al at one time 2 O 3 The surface can also be coated with alpha-Al in batches 2 O 3 A surface. In some embodiments, step (1) is performed twice by first loading a portion (e.g., half) of the soluble magnesium-containing compound on α -Al 2 O 3 And (3) carrying out surface calcination to obtain an intermediate carrier, and then loading the residual soluble magnesium-containing compound on the surface of the intermediate carrier, and carrying out calcination to obtain the final carrier. The carrier is prepared by repeating the step (1) for multiple times, is suitable for preparing the carrier with higher MgO loading capacity, and is beneficial to the uniform coating of MgO on alpha-Al 2 O 3 And the conversion rate and OPP selectivity of the hydrogenation reaction are improved.
The soluble compound containing the active component is selected from one or more of a soluble platinum-containing compound, a soluble palladium-containing compound and a soluble rhodium-containing compound. In some embodiments, the active component is elemental platinum and the soluble compound comprising the active component is a soluble platinum-containing compound. The soluble platinum-containing compound suitable for use in the present invention may be one or more selected from chloroplatinic acid, tetraammineplatinum nitrate and tetraammineplatinum chloride. The soluble compound containing the active ingredient may be supported on the surface of the carrier by formulating the soluble compound containing the active ingredient into an aqueous solution and contacting the carrier with the aqueous solution of the soluble compound containing the active ingredient. The concentration of the active component (e.g., Pt ions) in an aqueous solution of a soluble compound containing the active component (e.g., an aqueous solution of a soluble platinum-containing compound, an aqueous solution of chloroplatinic acid) may be in the range of 0.5 to 2 wt%, e.g., 1 ± 0.2 wt%. The support may be contacted with the aqueous solution of the soluble compound containing the active ingredient by spraying or dipping. Spraying or impregnation may be carried out under heat (e.g. 20-70 c) to promote adsorption of the carrier to the aqueous solution containing the soluble compound of the active component and to allow some drying to occur during contact. For example, spraying may be accompanied by forced air drying, the temperature of the forced air may be 20-70 deg.C, for example 50 + -10 deg.C. The blowing is mainly to dry the material to a certain extent while loading so as to make the carrier have better effect of adsorbing the aqueous solution of the soluble compounds containing the active components. After loading by adopting the immersion method, stirring and evaporating at 80 +/-20 ℃. In some embodiments, the loading operation (e.g., spray plus forced air drying) of step (2) is performed in a sugar coater, a ball roller, or a rotary compounder. The rotating speed of the sugar-coating machine, the ball rolling machine or the rotary mixer is preferably 5-40 rpm. The use of sugar coating machines, ball rollers or rotary blenders for loading is beneficial to industrial scale-up. The rotating speed is set to be 5-40 rpm, so that the materials can be rolled in the machine, the purpose of fully and uniformly loading is achieved, and meanwhile, material abrasion caused by too fast speed is avoided.
After the soluble compound containing the active component is loaded on the surface of the carrier, the carrier can be dried to obtain the catalyst precursor. The carrier may be dried at 60 to 120 deg.C, for example 80 + -10 deg.C, for 5 to 16 hours, for example 12 + -2 hours.
The catalyst used in the present invention can be prepared by calcining a catalyst precursor. In the present invention, the manner of calcining the catalyst precursor is as follows: heating the mixture from room temperature to 500-700 deg.C, for example 600 + -50 deg.C, at a heating rate of 3-10 deg.C/min, for example 5 + -1 deg.C/min, and then calcining the mixture at the heated temperature for 2-8 h, for example 2-3 h. According to the invention, the heating rate is controlled to be 3-10 ℃/min, so that the phenomenon that the loaded components are evaporated or decomposed too fast in the roasting process to influence the uniformity of the final load can be prevented; meanwhile, the roasting time and energy consumption are prevented from being increased due to too slow temperature rise. According to the invention, the roasting constant temperature is controlled to be 500-700 ℃, the time is controlled to be 2-8 h, and the load components can be fully decomposed within the shortest time of minimum energy consumption.
The catalyst obtained after the catalyst precursor is roasted is an unactivated catalyst. The activated catalyst may be obtained by reducing an unactivated catalyst. In the present invention, the activation of the hydrogenation catalyst can be achieved by reacting the hydrogenation catalyst with a reducing agent at a certain temperature. The reduction reaction is usually carried out in the presence of a reducing agent. The reducing agent may be a reducing atmosphere such as hydrogen gas. The flow rate of the hydrogen gas may be 5 to 15L/min, for example 8. + -.1L/min. The temperature of the reduction reaction can be 350-450 ℃, for example 400 +/-20 ℃. The time of the reduction reaction can be 2-6 h, such as 4 +/-1 h. The rate of the temperature rise from room temperature to the reduction reaction temperature during the reduction reaction may be 3 to 10 ℃/min, for example, 5. + -. 1 ℃/min. The pressure during the reduction reaction may be from 0.5MPa to 2MPa, preferably from 0.7MPa to 1.5MPa, for example 1.2. + -. 0.2 MPa.
The process of the present invention for the preparation of o-phenylphenol comprises subjecting dibenzofuran to a hydrogenation reaction in the presence of the catalyst described herein. If the hydrogenation catalyst used in the hydrogenation reaction is a hydrogenation catalyst which has not been activated, the catalyst is subjected to the aforementioned activation treatment before the hydrogenation reaction. The hydrogenation reaction may be carried out in a fixed bed reactor.
In the present invention, the dibenzofuran starting material used for the hydrogenation reaction may be a dibenzofuran solution or dibenzofuran, that is, the dibenzofuran starting material may be provided in the form of a dibenzofuran solution or molten dibenzofuran. It is understood that the dibenzofuran starting material herein refers to the material form of dibenzofuran as it enters the reaction system. The dibenzofuran raw material is dibenzofuran (namely, the concentration of the dibenzofuran raw material is 100%), which means that dibenzofuran is not dissolved in a solvent and directly enters a reaction system. The dibenzofuran raw material is dibenzofuran solution, which means that dibenzofuran is dissolved in a solvent and then enters a reaction system. In the present invention, the concentration of the dibenzofuran solution as the dibenzofuran raw material may be 10% to 100%. The method is particularly suitable for using the dibenzofuran solution with higher concentration as the dibenzofuran raw material. In some embodiments, the mass fraction of dibenzofuran in the dibenzofuran solution is greater than 35%, for example, may be greater than 40%, greater than 50%, greater than 60%, greater than 70%, for example, 35% -100%, 40% -100%, 50% -70%. Thanks to the catalyst used in the present invention, the reaction has high dibenzofuran conversion rate and OPP selectivity even if a high concentration dibenzofuran starting material (for example, dibenzofuran solution with mass fraction of more than 35%) is used. The invention discovers that the dibenzofuran solution with the mass fraction of 35-100 percent, particularly 50-70 percent can obtain very good comprehensive effects of high dibenzofuran conversion rate and high OPP selectivity, and simultaneously, under the condition of high-concentration dibenzofuran raw material, the used solvent amount is greatly reduced, correspondingly, the process energy consumption and the device investment are greatly reduced, and the economic benefit is obvious. In the present invention, the solvent for dissolving dibenzofuran may be an alkane containing 4 to 9 carbon atoms or an aromatic hydrocarbon containing 6 to 9 carbon atoms, preferably selected from one or more of hexane, cyclohexane, benzene, toluene and xylene. In some embodiments, the solvent of the dibenzofuran solution is toluene. Herein, alkanes include paraffins and naphthenes.
In the present invention, the dibenzofuran feed rate is determined according to the catalyst activity requirement, and generally, the dibenzofuran feed rate should be adjusted so that the mass space velocity of dibenzofuran is 0.4h -1 -2h -1 E.g. 0.5h -1 -1.5h -1 Preferably 0.7h -1 -1.5h -1 E.g. 0.8. + -. 0.1h -1 . Herein, the dibenzofuran mass space velocity is equal to dibenzofuran mass flow rate/catalyst mass. When the dibenzofuran is fed as a dibenzofuran solution, the mass space velocity of the dibenzofuran calculated as above does not contain any solvent mass. Introducing hydrogen during hydrogenation reaction. The hydrogen flow rate should be such that the ratio of the mass of hydrogen to the mass of dibenzofuran is greater than 0.12, preferably the ratio of the mass of hydrogen to the mass of dibenzofuran is from 0.3 to 2, for example 0.4. + -. 0.05. The reactor may be preheated prior to the hydrogenation reaction. The preheating temperature may be 250 ℃ to 450 ℃, preferably 350 ℃ to 400 ℃. The reaction temperature for the hydrogenation reaction may be in the range of 300 ℃ to 450 ℃, preferably 350 ℃ to 420 ℃, for example 410 ± 10 ℃. The pressure during the hydrogenation reaction may be from 0.5MPa to 2MPa, preferably from 0.7MPa to 1.5MPa, for example 1.2. + -. 0.1 MPa.
In some embodiments, the dibenzofuran raw material is pumped into a preheater by a liquid inlet pump for gasification, mixed with hydrogen, heated and then fed into a fixed bed reactor together for catalytic reaction.
And (3) carrying out alkali washing and acidification treatment on a reaction product of the hydrogenation reaction to obtain an OPP crude product, and recrystallizing to obtain an OPP finished product. The reaction product may be initially cooled prior to the caustic wash. The alkali washing may be performed using an aqueous solution of a strong base such as sodium hydroxide or potassium hydroxide, preferably an aqueous sodium hydroxide solution. The mass fraction of the aqueous sodium hydroxide solution may be between 0.5% and 15%, preferably 10. + -. 2%. The mass ratio of the alkali liquor to the product solution can be determined according to factors such as the concentration of the dibenzofuran raw material, the concentration of the alkali liquor, the generation amount of wastewater and the quality requirement of products, and is usually between 0.1 and 3, such as 0.3 +/-0.05. The present invention preferably subjects the reaction product to multiple alkaline washes. The multistage alkali washing is adopted, so that the generation amount of wastewater can be greatly reduced, and the yield and the purity of the product are improved. In the invention, the multistage alkali washing refers to alkali washing by using two or more extraction towers which are connected in series in sequence, wherein the product solution flows from the first extraction tower to the last extraction tower in sequence, and the fresh alkali solution flows from the last extraction tower to the first extraction tower in sequence. In the present invention, an extraction tower (also called a caustic washing extraction tower) has a meaning known in the art, and is a device for subjecting a product solution to caustic washing. In some embodiments, the present invention performs a two-stage caustic wash of the reaction product, i.e., a caustic wash using two extraction towers in series, with the product solution flowing from the first extraction tower to the second extraction tower and fresh lye flowing from the second extraction tower to the first extraction tower. In each extraction tower, the organic phase and the alkaline solution are fully mixed and extracted, wherein the organic phase flows to the last extraction tower according to the sequence of the extraction towers, and the aqueous phase flows to the first extraction tower according to the reverse sequence of the extraction towers. The organic phase flows out of the last extraction tower for solvent recovery. And (4) flowing out of the alkaline washing solution in a first extraction tower for acidification treatment to obtain a crude OPP product. The acidification can be carried out using hydrochloric acid or sulfuric acid. The mass fraction of hydrochloric acid or sulfuric acid may be 0.5% to 15%, preferably 10 ± 2%. And recrystallizing the OPP crude product to obtain the OPP finished product.
The method is adopted to catalyze the hydrogenation of the dibenzofuran to prepare the o-phenylphenol, the conversion rate of the dibenzofuran can reach more than 35%, more than 40%, more than 41%, more than 42%, more than 43%, more than 44% or more than 45%, the OPP selectivity can reach more than 80%, more than 81%, more than 83%, more than 84%, more than 85% or more than 86%, and the stable reaction running time can reach more than 500h or more than 4000 h. In some embodiments, the dibenzofuran raw material is a dibenzofuran solution with a concentration of more than 35%, for example, more than 40%, 50% -70%, and the method of the present invention is used to catalyze the hydrogenation of dibenzofuran to prepare o-phenylphenol, wherein the dibenzofuran conversion rate is more than 40%, more than 41%, more than 42%, more than 43%, more than 44% or more than 45%, the OPP selectivity is more than 80%, more than 81%, more than 83%, more than 84%, more than 85% or more than 86%, and the reaction stable operation time is more than 500h or more than 4000 h.
The invention has the following advantages:
1. the invention provides that high-concentration dibenzofuran is used as a raw material, so that the conversion rate of dibenzofuran reaction and the OPP selectivity are not reduced while the energy consumption is greatly reduced.
2. The method uses a multistage extraction method to separate the product by acid and alkali to obtain OPP, thereby greatly reducing the production amount of wastewater and simultaneously improving the yield and purity of the product.
3. The catalyst used by the invention can stably run for more than 4000 hours, has industrial conditions and has high economic value. The composite carrier of the catalyst used in the invention adopts the formed inert alpha-Al 2 O 3 The material has the characteristics of high strength, good stability, inertia, low specific surface area and the like. MgO/alpha-Al used in the present invention 2 O 3 The composite oxide carrier has the characteristics of alkalinity and low specific surface area, is beneficial to dispersing more active metals on the outer surface of the carrier and reducing the dosage of noble metals; the diffusion of reaction products is facilitated, and the OPP selectivity is improved; the alkalinity of the catalyst is also beneficial to reducing the generation of byproducts and improving the OPP selectivity.
4. The catalyst used in the invention has less noble metal consumption, which is beneficial to reducing the reaction cost.
5. The method disclosed by the invention is used for catalyzing the hydrogenation of the dibenzofuran to prepare the OPP, the conversion rate of the dibenzofuran is high, the selectivity to the OPP is high, the reaction is stable, the running time is long, the method is suitable for high-concentration dibenzofuran raw materials, the solvent consumption can be greatly reduced, and the energy consumption is further greatly reduced.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise indicated, conventional in the art. The starting compounds in the preparation examples are all commercially available.
Preparation example 1: catalyst preparation
Taking 100g of strip-shaped alpha-Al with the diameter of 3mm 2 O 3 Putting the mixture into a sugar-coating machine, slowly spraying 110g of a magnesium nitrate aqueous solution with the mass fraction of 32% onto the surface of a carrier at the rotating speed of 30r/min, in the whole spraying process, starting the sugar-coating machine by blowing air and keeping the air temperature at 50 ℃, taking out the carrier after the spraying of the magnesium nitrate solution is finished, drying the carrier at 100 ℃ for 5h, putting the dried sample into a muffle furnace for roasting, heating the dried sample to 600 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting the roasted carrier at 600 ℃ for 5h, taking out the carrier, putting the carrier into the sugar-coating machine at the rotating speed of 30r/min, spraying and soaking the 110g of the magnesium nitrate aqueous solution with the mass fraction of 32% onto the carrier again, in the whole spraying process, starting the air blowing of the sugar-coating machine and keeping the air temperature at 50 ℃, taking out the carrier after the spraying of the magnesium nitrate solution is finished, drying the carrier at 100 ℃ for 5h, putting the dried sample into the muffle furnace for roasting, heating from room temperature to 600 ℃ at a heating rate of 5 ℃/min, and then roasting at 600 ℃ for 5 hours to obtain MgO-Al 2 O 3 Composite carrier having a MgO content of about 16 wt%, alpha-Al 2 O 3 The content is about 84 wt%.
100g of the composite carrier is put into a sugar-coating machine, the rotating speed of the sugar-coating machine is 25r/min, 50g of chloroplatinic acid aqueous solution with the Pt mass fraction of 1% is slowly sprayed onto the surface of the carrier, in the whole spraying process, the sugar-coating machine is started by blowing air and kept at the wind temperature of 50 ℃, after the chloroplatinic acid aqueous solution is sprayed, the carrier is taken out, dried for 12 hours at the temperature of 80 ℃, a dried sample is put into a muffle furnace for roasting, the temperature is increased from the room temperature to 600 ℃ at the temperature rising rate of 5 ℃/min, and then the roasting is carried out at the temperature of 600 ℃ for 2 hours, so that the catalyst with the Pt loading capacity of 0.5 wt% is obtained. As shown in fig. 1, the XRD spectrum of the catalyst shows that the Pt content of the catalyst is too low and the dispersion is high, so that no Pt peak is observed.
Examples 1 to 5
Activating the catalyst: 100g of the catalyst prepared in preparation example 1 was packed in a fixed bed, and hydrogen was introduced at a flow rate of 8L/min and a set pressure of 1.2MPa to activate the catalyst by raising the temperature of the catalyst to 400 ℃ at a rate of 5 ℃/min and maintaining the temperature at 400 ℃ for 4 hours.
The reaction process is as follows: as shown in the flow diagram of fig. 2, dibenzofuran toluene solutions (examples 1 to 4) or pure dibenzofuran (example 5) with different dibenzofuran concentrations (20% to 80%) are pumped into a preheater by a liquid feed pump for gasification, mixed with hydrogen, heated and then fed into a fixed bed reactor for catalytic reaction under the following reaction conditions: the mass space velocity (mass flow rate of dibenzofuran/mass of catalyst) of the dibenzofuran is 0.8h -1 The hydrogen flow rate satisfies the condition that the ratio of the mass of the hydrogen to the mass of the dibenzofuran is 0.4, the catalytic reaction temperature of the fixed bed is 410 ℃, and the reaction pressure is 1.2 MPa.
And (3) a separation process: and (2) carrying out two-stage alkaline washing on a reaction product from the fixed bed reactor by using a sodium hydroxide aqueous solution with the mass fraction of 10% of sodium hydroxide after primary cooling, wherein two alkaline washing extraction towers are sequentially connected in series, the product solution flows from the first extraction tower (the extraction tower 1) to the second extraction tower (the extraction tower 2), and the alkali liquor flows from the second extraction tower to the first extraction tower. The ratio of the amount (by mass) of the alkali solution to the mass of the product solution was 0.3. The organic phase in each extraction tower is fully mixed with the alkali liquor solution for extraction. The organic phase flows out of the second extraction tower to be subjected to solvent recovery. And (3) after the alkaline solution flows out of the first extraction tower, carrying out acidification treatment by using a sulfuric acid aqueous solution with the sulfuric acid mass fraction of 10% to obtain an OPP crude product, and recrystallizing to obtain an OPP finished product.
The dibenzofuran conversion, OPP selectivity and the purity of the OPP crude product obtained were determined at 500h of reaction run.
The dibenzofuran concentrations and reaction and isolation results of examples 1-5 are shown in table 1.
The results in table 1 show that the method of the present invention is adopted to prepare o-phenylphenol by catalytic hydrogenation of a high concentration dibenzofuran raw material, and good dibenzofuran conversion rate and OPP selectivity are obtained; when the concentration of the dibenzofuran is more than 40%, particularly about 50%, the dibenzofuran has high dibenzofuran conversion rate and OPP selectivity, and the solvent content is low, so that the solvent consumption can be greatly reduced, and the energy consumption is greatly reduced.
Table 1: dibenzofuran concentrations and reaction and isolation results for examples 1-5
| Dibenzofuran concentration/% | Dibenzofuran conversion/% | OPP selectivity/%) | Crude OPP purity/%) | |
| Example 1 | 20 | 45 | 85 | 99.0 |
| Example 2 | 40 | 42 | 84 | 98.9 |
| Example 3 | 60 | 45 | 85 | 99.1 |
| Example 4 | 80 | 44 | 83 | 98.7 |
| Example 5 | 100 | 41 | 86 | 98.8 |
Example 6
Catalyst activation, reaction and separation were carried out in the same manner as in examples 1 to 5 except that the dibenzofuran concentration in example 6 was 50%. The dibenzofuran conversion and OPP selectivity were measured at 4000h of reaction run. As a result, the dibenzofuran conversion was 44% and the OPP selectivity was 83%.
The result of example 6 shows that the method of the present invention has very high dibenzofuran conversion rate and OPP selectivity after the high concentration dibenzofuran raw material is continuously operated for 4000 hours, and the method of the present invention has very good long-term operation stability and is suitable for industrial production.
Example 7
The catalyst activation, reaction and separation were carried out in the same manner as in examples 1 to 5 except that the dibenzofuran concentration in example 7 was 60% and the separation process used a primary caustic washing process, i.e., only one caustic washing extraction tower. The dibenzofuran conversion, OPP selectivity and OPP crude product purity were determined at 500h of reaction run. As a result, the dibenzofuran conversion was 45%, the OPP selectivity was 85%, and the OPP crude product purity was 97.1%.
Comparative examples 1 to 5
The catalyst activation, reaction and separation were performed according to the methods of examples 1 to 5, except that the catalyst prepared by the following procedure was used in comparative examples 1 to 5:
preparing a solution with the mass fraction of 3% by using deionized water and chloroplatinic acid, and adding a magnesium oxide carrier, wherein the solid-to-liquid ratio is 1: stirring for 6h at the temperature of 20 and 80 ℃, filtering and drying, and roasting the catalyst for 4h at the temperature of 500 ℃ in the air atmosphere to prepare the Pt/MgO catalyst, wherein the loading amount of the active component platinum is 0.5 wt%.
The dibenzofuran conversion, OPP selectivity and purity of the resulting crude OPP were measured at 50h of reaction run and the results are shown in table 2.
Table 2: results of reaction and isolation of comparative examples 1-5
| Dibenzofuran concentration/% | Dibenzofuran conversion/% | OPP selectivity/%) | Crude OPP purity/%) | |
| Comparative example 1 | 20 | 35 | 80 | 99.0 |
| Comparative example 2 | 40 | 40 | 54 | 99.0 |
| Comparative example 3 | 50 | 38 | 42 | 99.0 |
| Comparative example 4 | 60 | 36 | 35 | 99.0 |
| Comparative example 5 | 70 | 43 | 27 | 99.0 |
As can be seen from Table 2, when the Pt/MgO catalyst is used for catalyzing dibenzofuran to prepare o-phenylphenol, the dibenzofuran conversion rate and OPP selectivity are low when the dibenzofuran concentration is 20%; when the dibenzofuran concentration reached above 40%, the reaction was run for 50h with a significant reduction in OPP selectivity, indicating that the Pt/MgO catalyst had deactivated at this time. Therefore, the effect of catalyzing dibenzofuran by using the Pt/MgO catalyst to prepare o-phenylphenol is poor, and the Pt/MgO catalyst is not suitable for catalyzing the reaction of preparing o-phenylphenol by using a high-concentration dibenzofuran raw material.
Comparative examples 6 to 9
Catalyst activation, reaction and separation were carried out according to the methods of examples 1-5, except that: comparative examples 6 and 7 use the α -Al of preparation example 1 2 O 3 Replaced by strip-shaped gamma-Al with the diameter of 3mm 2 O 3 Catalyst prepared in the same manner as in preparation example 1 except for the preparation method (the MgO content in the carrier of the catalyst is about 16 wt%; gamma-Al) 2 O 3 Content about 84%, Pt loading about 0.5 wt%); comparative examples 8 and 9 use the α -Al of preparation example 1 2 O 3 Replacement by spherical theta-Al with a diameter of 3mm 2 O 3 Catalyst prepared in the same manner as in preparation example 1 except for the preparation method (the MgO content in the carrier of the catalyst is about 16 wt%; theta-Al) 2 O 3 The content was about 84% and the Pt loading was about 0.5 wt%). The dibenzofuran concentrations and reaction and isolation results of comparative examples 6-9 are shown in table 3.
Table 3: dibenzofuran concentrations and reaction and isolation results of comparative examples 6-9
| Dibenzofuran concentration/% | Dibenzofuran conversion/% | OPP selectivity/%) | Crude OPP purity/%) | |
| Comparative example 6 | 40 | 31 | 69 | 99.1 |
| Comparative example 7 | 60 | 29 | 60 | 99.0 |
| Comparative example 8 | 40 | 27 | 71 | 99.3 |
| Comparative example 9 | 60 | 25 | 75 | 98.7 |
As can be seen by comparing Table 1 and Table 3, MgO-gamma-Al is used 2 O 3 Or MgO-theta-Al 2 O 3 The catalyst used as the carrier catalyzes a dibenzofuran raw material with the concentration of 40 percent or 60 percent to prepare o-phenylphenol, and the dibenzofuran conversion rate and the OPP selectivity are lower. The method of the invention uses MgO-alpha-Al 2 O 3 The catalyst used as the carrier catalyzes the dibenzofuran raw material with the concentration of 40 percent or 60 percent to prepare the o-phenylphenol, and compared with the comparative ratio of 6-9, the dibenzofuran conversion rate and the OPP selectivity are obviously improved. Compared with methods using other catalysts, the method for preparing o-phenylphenol by catalyzing high-concentration dibenzofuran raw materials has a very good reaction effect, can remarkably improve the reaction efficiency and the product yield, and simultaneously realizes great reduction of energy consumption.
Preparation example 2: catalyst preparation
The catalyst of preparation example 1 was prepared by the same preparation method as in preparation example 1 except that the amount of the chloroplatinic acid aqueous solution having a Pt mass fraction of 1% in preparation example 1 was changed to 60 g. The catalyst has a carrier with an MgO content of about 16 wt%, alpha-Al 2 O 3 The content is about 84 wt%. The Pt loading of the catalyst was 0.6 wt%.
Example 8
Catalyst activation, reaction and separation were carried out in the same manner as in examples 1 to 5, except that the catalyst used in example 8 was the catalyst of preparation example 2 and the dibenzofuran concentration was 60%. The dibenzofuran conversion, OPP selectivity and OPP crude product purity were determined at 500h of reaction run. As a result, the dibenzofuran conversion was 46%, the OPP selectivity was 83%, and the OPP crude product purity was 99.0%.
Claims (10)
1. A process for the preparation of o-phenylphenol, comprising subjecting dibenzofuran to a hydrogenation reaction in the presence of a catalyst comprisingComprises a carrier and an active component with catalytic function, wherein the carrier comprises alpha-Al 2 O 3 And MgO, the active component including one or more selected from platinum element, palladium element and rhodium element.
2. The process of claim 1, wherein the hydrogenation reaction is carried out in a fixed bed reactor.
3. The process according to claim 1, wherein the dibenzofuran starting material used in the process is pure dibenzofuran or a dibenzofuran solution with a dibenzofuran mass fraction > 35%, preferably a dibenzofuran solution with a dibenzofuran mass fraction of 50% to 70%, the solvent of the dibenzofuran solution being preferably selected from alkanes containing 4 to 9 carbon atoms and aromatic hydrocarbons containing 6 to 9 carbon atoms, more preferably from one or more of hexane, cyclohexane, benzene, toluene and xylene.
4. The method of claim 1, wherein the method has one or more of the following features:
in the hydrogenation reaction, the mass space velocity of the dibenzofuran is 0.4h -1 -2h -1 Preferably 0.7h -1 -1.5h -1 ；
In the hydrogenation reaction, the ratio of the mass of hydrogen to the mass of dibenzofuran is more than 0.12: 1, preferably (0.3-2): 1;
the preheating temperature of the hydrogenation reaction is 250-450 ℃, and preferably 350-400 ℃;
the reaction temperature of the hydrogenation reaction is 300-450 ℃, and preferably 350-420 ℃; and
the reaction pressure of the hydrogenation reaction is 0.5MPa-2MPa, preferably 0.7MPa-1.5 MPa.
5. The method of claim 1, wherein the method has one or more of the following features:
the active component is platinum element;
in the carrier, alpha-Al 2 O 3 The mass of the carrier is 70 to 96 percent of the total mass of the carrierThe mass of MgO accounts for 4-30% of the total mass of the carrier; preferably, in the carrier, α -Al 2 O 3 The mass of the MgO accounts for 76-95% of the total mass of the carrier, and the mass of the MgO accounts for 5-24% of the total mass of the carrier;
in the catalyst, the mass of the active component is 0.1-20%, preferably 0.2-10% of the mass of the carrier; and
in the catalyst, the MgO is positioned in the alpha-Al 2 O 3 Of (2) is provided.
6. The method of claim 1, wherein the catalyst is prepared by a method comprising:
(1) loading soluble magnesium-containing compound on alpha-Al 2 O 3 Surface, calcining to obtain a carrier;
(2) loading a soluble compound containing an active component on the surface of the carrier to obtain a catalyst precursor;
(3) and calcining the catalyst precursor.
7. The method of claim 6, wherein the method has one or more of the following features:
the soluble magnesium-containing compound is selected from one or more of magnesium nitrate, magnesium acetate and magnesium chloride;
in the step (1), a sugar-coating machine, a ball rolling machine or a rotary mixer is used for carrying out the loading, and the rotating speed of the sugar-coating machine, the ball rolling machine or the rotary mixer is preferably 5-40 rpm;
in the step (1), soluble magnesium-containing compound is loaded on alpha-Al by adopting a spraying or dipping mode 2 O 3 A surface;
the calcining mode in the step (1) is as follows: heating the mixture from room temperature to 500-700 ℃ at a heating rate of 3-10 ℃/min, and then roasting for 2-8 h;
in the step (1), before calcination, alpha-Al loaded with soluble magnesium-containing compound is subjected to calcination 2 O 3 Drying, wherein the drying is preferably carried out for 5-16 h at the temperature of 60-120 ℃;
the soluble compound containing the active component is selected from one or more of soluble platinum-containing compounds, soluble palladium-containing compounds and soluble rhodium-containing compounds, and the soluble platinum-containing compounds are selected from one or more of chloroplatinic acid, tetraammineplatinum nitrate and tetraammineplatinum chloride;
in the step (2), a sugar-coating machine, a ball rolling machine or a rotary mixer is used for carrying out the loading, and the rotating speed of the sugar-coating machine, the ball rolling machine or the rotary mixer is preferably 5-40 rpm;
in the step (2), soluble compounds containing active components are loaded on the surface of the carrier in a spraying or dipping mode;
the step (2) also comprises the step of drying the carrier loaded with the soluble compound containing the active component, wherein the drying is preferably carried out for 5-16 h at the temperature of 60-120 ℃;
the calcining mode in the step (3) is as follows: heating from room temperature to 500-700 ℃ at a heating rate of 3-10 ℃/min, and then roasting for 2-8 h.
8. The method of claim 6, wherein the method of preparing the catalyst further comprises the steps of:
(4) and (4) reducing the catalyst obtained in the step (3) for 2-6 h at the temperature of 350-450 ℃.
9. The process of claim 1, further comprising subjecting the product solution of the hydrogenation reaction to multiple caustic washes, wherein fresh caustic is mixed with the organic phase subjected to the last stage of caustic wash, and then the caustic wash is mixed in reverse order with the organic phase subjected to each stage of caustic wash.
10. The method of claim 1, wherein the ratio of the mass of lye to product solution is (0.1-3): 1.
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| CN104841421A (en) * | 2015-04-15 | 2015-08-19 | 北京旭阳化工技术研究院有限公司 | Catalyst composition and preparation method thereof, and method for preparing o-phenylphenol by using catalyst composition |
| CN105879862A (en) * | 2016-04-22 | 2016-08-24 | 大连理工大学 | Preparation method of eggshell-type noble metal catalyst and method of using same for dibenzofuran hydrogenation ring opening to prepare o-phenylphenol |
| CN106478378A (en) * | 2016-08-31 | 2017-03-08 | 大连理工大学 | A kind of low pressure hydrogen vaporizes the method that dibenzofuran is hydrogenated with open loop o-phenyl phenol |
| CN109999832A (en) * | 2019-04-30 | 2019-07-12 | 山西中科化美科技有限责任公司 | The method for preparing catalyst of o-phenyl phenol is prepared for dibenzofurans plus hydrogen |
| CN111153771A (en) * | 2020-01-20 | 2020-05-15 | 荣成青木高新材料股份有限公司 | Method for preparing o-phenylphenol by directly catalyzing and hydrogenating dibenzofuran |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841421A (en) * | 2015-04-15 | 2015-08-19 | 北京旭阳化工技术研究院有限公司 | Catalyst composition and preparation method thereof, and method for preparing o-phenylphenol by using catalyst composition |
| CN105879862A (en) * | 2016-04-22 | 2016-08-24 | 大连理工大学 | Preparation method of eggshell-type noble metal catalyst and method of using same for dibenzofuran hydrogenation ring opening to prepare o-phenylphenol |
| CN106478378A (en) * | 2016-08-31 | 2017-03-08 | 大连理工大学 | A kind of low pressure hydrogen vaporizes the method that dibenzofuran is hydrogenated with open loop o-phenyl phenol |
| CN109999832A (en) * | 2019-04-30 | 2019-07-12 | 山西中科化美科技有限责任公司 | The method for preparing catalyst of o-phenyl phenol is prepared for dibenzofurans plus hydrogen |
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