CN116586071A - Catalyst for preparing methyl phenylcarbamate and preparation method and application thereof - Google Patents
Catalyst for preparing methyl phenylcarbamate and preparation method and application thereof Download PDFInfo
- Publication number
- CN116586071A CN116586071A CN202310598434.5A CN202310598434A CN116586071A CN 116586071 A CN116586071 A CN 116586071A CN 202310598434 A CN202310598434 A CN 202310598434A CN 116586071 A CN116586071 A CN 116586071A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- urea
- preparing
- transition metal
- combination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- IAGUPODHENSJEZ-UHFFFAOYSA-N methyl n-phenylcarbamate Chemical compound COC(=O)NC1=CC=CC=C1 IAGUPODHENSJEZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004202 carbamide Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- -1 transition metal salt Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 29
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229940095102 methyl benzoate Drugs 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 10
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 10
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 238000006136 alcoholysis reaction Methods 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing methyl phenyl carbamate, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing the carrier, the transition metal salt, the precipitant and water for reaction, and then filtering, drying and roasting to obtain the catalyst. The catalyst provided by the invention is applied to the synthesis of methyl phenyl carbamate by mixed urea, the conversion rate of the mixed urea is more than 98.5%, the yield of the methyl phenyl carbamate is more than 98%, the catalyst has high activity and good stability, and the high-selectivity synthesis of the methyl phenyl carbamate by the mixed urea is realized.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a catalyst for preparing methyl phenyl carbamate, a preparation method and application thereof, in particular to a catalyst for preparing methyl phenyl carbamate, which has high yield and good stability, and a preparation method and application thereof.
Background
Methyl benzoate (MPC) is an intermediate for the synthesis of diphenylmethane diisocyanate (MDI), which is one of the important raw materials for the synthesis of polyurethane. The main production method of MDI is phosgene method, which has (1) extremely toxic raw materials and pollutes the environment; (2) by-product hydrochloric acid etching equipment; (3) The product contains the defects of difficult free chlorine removal and the like, so the non-phosgene method for synthesizing MDI becomes a focus of attention of researchers at home and abroad. At present, various methods for synthesizing MPC are reported, such as oxidative carbonylation of aniline, aniline and CO 2 And a methanol one-step method, a diphenylurea alcoholysis method, a nitrobenzene reductive carbonylation method, a one-step method of aniline, urea and methanol, a dimethyl carbonate (DMC) amination method, and the like. The catalysts of the oxidative carbonylation method and the reductive carbonylation method are noble metal catalysts, and the catalyst cost is high; in addition, potential safety hazards exist in the oxidative carbonylation method for carbon monoxide and oxygen, the utilization rate of carbon monoxide in the reductive carbonylation method is low, the carbon monoxide and the carbon dioxide are difficult to separate, and the production cost is high; one-step methods generally have low MPC yields and limited industrialization. At present, diphenyl urea (DPU) alcoholysis and DMC (DMC) amination are a greener and safer route, DMC amination catalysts are mainly homogeneous catalysts or lead-containing catalysts, and although higher MPC selectivity can be obtained, the homogeneous catalysts are easy to deactivate and difficult to recover, and heterogeneous oxide catalysts have lower MPC selectivity. The diphenyl urea alcoholysis method mainly adopts catalysts such as lead-containing oxide or fluoride, is easy to cause harm to the environment, and the highest MPC yield is only 84%. Diphenylurea is usually formed by heating and condensing aniline and urea, phenyl Urea (PU) is often generated in the reaction process, and PU is also a raw material for synthesizing MPC through alcoholysis, and the prior art is not directed atA high-efficiency alcoholysis method of mixed urea composed of DPU and PU.
Therefore, it is necessary to develop a heterogeneous catalyst which is environmentally friendly and has high activity and stability for synthesizing methyl benzoate by mixed urea alcoholysis.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst for preparing methyl benzoate and a preparation method and application thereof, in particular to a catalyst for preparing methyl benzoate with high yield and good stability and a preparation method and application thereof. The catalyst provided by the invention is applied to the synthesis of methyl phenyl carbamate by mixed urea, the conversion rate of the mixed urea is more than 98.5%, the yield of the methyl phenyl carbamate is more than 98%, the catalyst has high activity and good stability, and the high-selectivity synthesis of the methyl phenyl carbamate by the mixed urea is realized.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a catalyst for the preparation of methyl phenylcarbamate, the method comprising the steps of: mixing the carrier, the transition metal salt, the precipitant and water for reaction, and then filtering, drying and roasting to obtain the catalyst.
The catalyst provided by the invention is applied to the synthesis of methyl phenyl carbamate by mixed urea, the conversion rate of the mixed urea is more than 98.5%, the yield of the methyl phenyl carbamate is more than 98%, the catalyst has high activity and good stability, and the high-selectivity synthesis of the methyl phenyl carbamate by the mixed urea is realized.
Preferably, the support comprises any one or a combination of at least two of alumina, silica or magnesia, for example, a combination of alumina and silica, a combination of silica and magnesia or a combination of alumina and magnesia, etc., but is not limited to the above-listed combinations, and other non-listed combinations within the above-listed ranges are equally applicable, preferably a combination of silica and magnesia.
The specific carrier can be effectively combined with the transition metal salt, so that the stability of the catalyst is improved.
Preferably, the transition metal salt includes any one or a combination of at least two of chloride, nitrate, carbonate, acetate or oxalate of a transition metal, for example, a combination of chloride and nitrate of a transition metal, a combination of chloride and carbonate of a transition metal, or a combination of carbonate and acetate of a transition metal, etc., but not limited to, the above-listed combinations, and other non-listed combinations within the above-listed combinations are equally applicable, preferably a combination of chloride and nitrate of a transition metal.
Preferably, the transition metal in the transition metal salt includes any one or a combination of at least two of Ce, zr, zn, mn, ti, ni or Co, for example, a combination of Ce and Zr, a combination of Zr and Zn, or a combination of Ti and Mn, etc., but is not limited to the above-listed combinations, and other non-listed combinations within the above-listed combinations are equally applicable, preferably a combination of Ce, zr and Co.
The specific transition metal salt can be effectively combined with a carrier, so that the stability of the catalyst is improved.
Preferably, the precipitant includes any one or a combination of at least two of urea, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate or potassium bicarbonate, for example, a combination of urea and sodium hydroxide, a combination of sodium hydroxide and potassium hydroxide, or a combination of sodium bicarbonate and sodium carbonate, etc., but is not limited to the above-listed combinations, and other non-listed combinations within the above-listed combinations are equally applicable.
Preferably, the mole ratio of the transition metal salt, the carrier and the precipitant is 1 (2-50): 4-20.
Preferably, the mass ratio of water to carrier is (10-100): 1.
Preferably, the temperature of the reaction is 60-180 ℃ and the time is 6-48h.
Preferably, the roasting temperature is 300-700 ℃ and the time is 3-12h.
Wherein, in the molar ratio of the transition metal salt, the carrier and the precipitant, the proportion of the carrier can be 2, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50, etc., the proportion of the precipitant can be 4, 6, 8, 10, 12, 14, 16, 18 or 20, etc., the mass ratio of water to the carrier can be 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, etc., the reaction temperature can be 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃ and the like, the time may be 6h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h, etc., the baking temperature may be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ etc., and the time may be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, etc., but not limited to the above-listed values, and other non-listed values within the above-listed ranges are equally applicable.
Preferably, the reaction is carried out in a precipitation tank.
In a second aspect, the present invention provides a catalyst prepared by the preparation method described above.
In a third aspect, the present invention also provides a method for preparing methyl benzoate, the method comprising the steps of: and mixing the catalyst, mixed urea and methanol for reaction to obtain the methyl phenylcarbamate.
Preferably, the mixed urea is a mixture of diphenyl urea and phenyl urea, wherein the molar ratio of diphenyl urea to phenyl urea is (2.5-64): 1.
Preferably, the molar ratio of the mixed urea to methanol is 1 (4-20).
Preferably, the mass ratio of the mixed urea to the catalyst is 1 (0.02-0.5).
Preferably, the temperature of the reaction is 120-180 ℃ and the time is 15-240min.
Wherein the molar ratio of diphenylurea to phenylurea may be 2.5:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1 or 64:1, etc., the molar ratio of mixed urea to methanol may be 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, etc., the mass ratio of mixed urea to catalyst may be 1:0.02, 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, etc., the temperature of the reaction may be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃ and the like, the time may be 15min, 60min, 180min, 210min, or the like, but the values are not limited to the above ranges, or the other values may be applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a catalyst for preparing methyl benzoate, which is applied to the synthesis of methyl benzoate from mixed urea, wherein the conversion rate of mixed urea is more than 98.5%, the yield of methyl benzoate is more than 98%, the catalyst has high activity and good stability, and the high-selectivity synthesis of methyl benzoate from mixed urea is realized; and the stability of the catalyst can be effectively improved by selecting a specific carrier and transition metal salt.
Drawings
FIG. 1 is a total ion chromatogram of the product of application example 1;
FIG. 2 is a secondary mass spectrum of the product of application example 1.
Detailed Description
In order to further describe the technical means adopted by the present invention and the effects thereof, the following describes the technical scheme of the present invention in combination with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
Example 1
The embodiment provides a catalyst, and the preparation method is as follows:
(1) 1.50g of silicon oxide, 1.01g of magnesium oxide, 0.87g of cerium nitrate hexahydrate, 0.86g of zirconium nitrate pentahydrate, 0.24g of cobalt chloride hexahydrate, 3.00g of urea and 50.19g of water are weighed, added into a precipitation kettle, the precipitation kettle is kept at 120 ℃ for 12 hours in an oven, and then the materials in the kettle are taken out, filtered, washed with water and dried at 100 ℃ for 12 hours to obtain a catalyst precursor.
(2) And (3) placing the catalyst precursor in the step (1) into a muffle furnace, and roasting at 500 ℃ for 3 hours to obtain the catalyst.
Example 2
The embodiment provides a catalyst, and the preparation method is as follows:
(1) 1.50g of silicon oxide, 1.01g of magnesium oxide, 1.30g of cerium nitrate hexahydrate, 0.43g of zirconium nitrate pentahydrate, 0.24g of cobalt chloride hexahydrate, 3.00g of urea and 50.19g of water are weighed, added into a precipitation kettle, the precipitation kettle is kept at 60 ℃ for 48 hours in an oven, and then the materials in the kettle are taken out, filtered, washed with water and dried at 100 ℃ for 12 hours to obtain a catalyst precursor.
(2) And (3) placing the catalyst precursor in the step (1) into a muffle furnace, and roasting at 700 ℃ for 3 hours to obtain the catalyst.
Example 3
The embodiment provides a catalyst, and the preparation method is as follows:
(1) 1.50g of silicon oxide, 1.01g of magnesium oxide, 0.43g of cerium nitrate hexahydrate, 0.43g of zirconium nitrate pentahydrate, 0.71g of cobalt chloride hexahydrate, 3.00g of urea and 50.19g of water are weighed, added into a precipitation kettle, the precipitation kettle is kept at 60 ℃ for 48 hours in an oven, and then the materials in the kettle are taken out, filtered, washed with water and dried at 100 ℃ for 12 hours to obtain a catalyst precursor.
(2) And (3) placing the catalyst precursor in the step (1) into a muffle furnace, and roasting at 700 ℃ for 3 hours to obtain the catalyst.
Example 4
This example provides a catalyst that is prepared in the same manner as example 1 except that no silica is added and a portion of the amount of magnesium oxide that is distributed to equimolar amounts is reduced.
Example 5
This example provides a catalyst that is prepared in the same manner as example 1 except that no magnesium oxide is added and a portion of the amount of silicon oxide that is distributed to an equimolar amount is reduced.
Example 6
This example provides a catalyst prepared in accordance with example 1 except that magnesia and silica were replaced with equimolar amounts of alumina.
Example 7
This example provides a catalyst that is prepared in the same manner as example 1 except that cerium nitrate hexahydrate is not added and a portion of the cerium nitrate hexahydrate is proportionally distributed to equimolar amounts of zirconium nitrate pentahydrate and cobalt chloride hexahydrate.
Example 8
This example provides a catalyst that is prepared in the same manner as example 1 except that zirconium nitrate pentahydrate is not added and a portion of the zirconium nitrate pentahydrate and cobalt chloride hexahydrate are proportionally distributed in equimolar amounts.
Example 9
This example provides a catalyst that is prepared in the same manner as example 1 except that cobalt chloride hexahydrate is not added and a portion of the cobalt chloride hexahydrate is proportionally distributed to equimolar amounts of zirconium nitrate pentahydrate and cerium nitrate hexahydrate.
Example 10
This example provides a catalyst that is prepared in the same manner as example 1 except that zirconium nitrate pentahydrate and cerium nitrate hexahydrate are not added, and that the partial distribution of equimolar amounts of cobalt chloride hexahydrate is reduced.
Example 11
This example provides a catalyst prepared in accordance with example 1 except zirconium nitrate pentahydrate, cerium nitrate hexahydrate and cobalt chloride hexahydrate were replaced with equimolar amounts of zirconium acetate, cerium acetate and cobalt oxalate, respectively.
Example 12
This example provides a catalyst prepared in accordance with example 1 except zirconium nitrate pentahydrate, cerium nitrate hexahydrate and cobalt chloride hexahydrate were replaced with equimolar amounts of zinc acetate dihydrate.
Application example 1
The application example provides a preparation method of methyl phenyl carbamate, which comprises the following specific steps:
2.12g of diphenylurea, 0.14g of phenylurea, 0.23g of the catalyst obtained in example 1 and 5.29g of methanol were weighed, added into a 50mL autoclave, magnetically stirred, at a reaction temperature of 160℃for 0.5h, and after the reaction was completed, the sample was examined by liquid chromatography (conversion and yield were calculated). And centrifuging the reaction solution, collecting supernatant, distilling the supernatant under reduced pressure to remove the solvent to obtain crude MPC, recrystallizing with cyclohexane to obtain MPC product, and detecting the MPC product by gas chromatography-mass spectrometry analysis, wherein the results are shown in figures 1 and 2. The results in FIGS. 1 and 2 show that the purity of MPC product reaches over 99.9%.
Application examples 2 to 12
Application examples 2 to 12 respectively provide a preparation method of methyl phenylcarbamate, and the specific steps are the same as those of application example 1 except that the catalysts obtained in example 1 are replaced by the catalysts obtained in examples 2 to 12 in equimolar amounts.
Catalyst effect evaluation:
the conversion of phenylurea, diphenylurea and MPC yield were counted in application examples 1 to 12 and the results were as follows:
| group of | Diphenylurea conversion/% | Phenylurea conversion/% | MPC yield/% |
| Application example 1 | 99.3 | 99.1 | 98.6 |
| Application example 2 | 99.2 | 98.9 | 98.3 |
| Application example 3 | 98.6 | 98.5 | 98.1 |
| Application example 4 | 91.3 | 90.8 | 90.4 |
| Application example 5 | 88.2 | 87.6 | 87.4 |
| Application example 6 | 73.5 | 72.8 | 72.1 |
| Application example 7 | 88.4 | 87.9 | 87.7 |
| Application example 8 | 88.1 | 87.4 | 87.4 |
| Application example 9 | 89.8 | 89.4 | 89.1 |
| Application example 10 | 87.2 | 86.7 | 86.7 |
| Application example 11 | 87.6 | 87.1 | 87.0 |
| Application example 12 | 92.3 | 91.9 | 91.8 |
The catalyst used in each application example was then recovered and reused for the preparation of methyl benzoate (see the original application example), the catalyst being reused a total of 20 times, the results of the 20 th use of each catalyst being as follows:
| group of | Diphenylurea conversion/% | Phenylurea conversion/% | MPC yield/% |
| Application example 1 | 99.2 | 99.1 | 98.5 |
| Application example 2 | 99.0 | 98.8 | 98.1 |
| Application example 3 | 98.2 | 98.2 | 97.7 |
| Application example 4 | 84.0 | 83.6 | 83.2 |
| Application example 5 | 80.2 | 79.5 | 79.4 |
| Application example 6 | 70.7 | 69.5 | 69.4 |
| Application example 7 | 80.0 | 79.5 | 79.3 |
| Application example 8 | 80.8 | 80.1 | 80.2 |
| Application example 9 | 75.3 | 75.0 | 74.8 |
| Application example 10 | 78.8 | 78.4 | 78.4 |
| Application example 11 | 70.2 | 69.8 | 69.7 |
| Application example 12 | 85.0 | 84.6 | 84.5 |
The result shows that the catalyst provided by the invention can effectively catalyze mixed urea to synthesize methyl benzoate, and has the characteristics of high raw material conversion rate and high yield; and comparing example 1 with examples 2-12, it can be found that the present invention improves the stability and service life of the catalyst by selecting a specific combination of the carrier and the transition metal salt so that the carrier and the transition metal salt can be effectively combined.
The applicant states that the catalyst for the preparation of methyl benzoate of the present invention, and its preparation method and application are illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (10)
1. A method for preparing a catalyst for preparing methyl phenylcarbamate, the method comprising the steps of: mixing the carrier, the transition metal salt, the precipitant and water for reaction, and then filtering, drying and roasting to obtain the catalyst.
2. The method for preparing a catalyst for methyl benzoate according to claim 1 characterized in that said support comprises any one or a combination of at least two of alumina, silica or magnesia, preferably a combination of silica and magnesia.
3. The method for preparing a catalyst for methyl benzoate according to claim 1 characterized in that said transition metal salt comprises any one or a combination of at least two of chloride, nitrate, carbonate, acetate or oxalate of transition metal, preferably a combination of chloride and nitrate of transition metal.
4. The method for preparing a catalyst for methyl benzoate according to claim 1 characterized in that the transition metal in the transition metal salt comprises any one or a combination of at least two of Ce, zr, zn, mn, ti, ni or Co, preferably Ce, zr and Co.
5. The method for preparing a catalyst for methyl benzoate according to claim 1, characterized in that said precipitant comprises any one or a combination of at least two of urea, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate or potassium bicarbonate.
6. The method for preparing a catalyst for methyl benzoate according to claim 1 characterized in that the molar ratio of transition metal salt, carrier to precipitant is 1 (2-50): 4-20;
the mass ratio of the water to the carrier is (10-100): 1;
the reaction temperature is 60-180 ℃ and the reaction time is 6-48h;
the roasting temperature is 300-700 ℃ and the roasting time is 3-12h.
7. The method for preparing a catalyst for methyl benzoate according to claim 1 characterized in that said reaction is performed in a precipitation tank.
8. A catalyst prepared by the method for preparing a catalyst for methyl benzoate according to any one of claims 1-7.
9. A method for preparing methyl benzoate, which is characterized by comprising the following steps: mixing the catalyst of claim 8, mixed urea and methanol to obtain the methyl phenylcarbamate.
10. The method for producing methyl phenylcarbamate according to claim 9, wherein the mixed urea is a mixture of diphenyl urea and phenyl urea, wherein the molar ratio of diphenyl urea to phenyl urea is (2.5 to 64): 1;
the molar ratio of the mixed urea to the methanol is 1 (4-20);
the mass ratio of the mixed urea to the catalyst is 1 (0.02-0.5);
the reaction temperature is 120-180 ℃ and the reaction time is 15-240min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310598434.5A CN116586071A (en) | 2023-05-25 | 2023-05-25 | Catalyst for preparing methyl phenylcarbamate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310598434.5A CN116586071A (en) | 2023-05-25 | 2023-05-25 | Catalyst for preparing methyl phenylcarbamate and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116586071A true CN116586071A (en) | 2023-08-15 |
Family
ID=87600534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310598434.5A Pending CN116586071A (en) | 2023-05-25 | 2023-05-25 | Catalyst for preparing methyl phenylcarbamate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116586071A (en) |
-
2023
- 2023-05-25 CN CN202310598434.5A patent/CN116586071A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0753470A (en) | Production of dialkyl carbonate | |
| CN104774148A (en) | Method used for preparing high-purity ethyl methyl carbonate | |
| US7518012B2 (en) | Process for the preparation of dialkyl carbonate | |
| CN103896811A (en) | Method for preparing 1,6-hexamethylene diurethane through heterogeneous catalysis | |
| JPS6125696B2 (en) | ||
| CN102964272B (en) | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase | |
| CN101845001B (en) | Heterogeneous catalytic method for preparing phenyl carbamate | |
| KR101470714B1 (en) | Process for production of zinc toluenesulfonate, zinc toluenesulfonate, and process for production of carbamate | |
| CN101328124B (en) | Ester exchange method for synthesizing ethylene diglycol diene propyl carbonic ether | |
| CN116586071A (en) | Catalyst for preparing methyl phenylcarbamate and preparation method and application thereof | |
| CN102600894B (en) | Method for preparing loaded organic acid zinc catalyst | |
| CN1185196C (en) | Process for producing ketoisophorone with additives | |
| CN108727193B (en) | Preparation method of diphenyl carbonate compound | |
| CN102531908B (en) | The preparation method of methyl benzol carbonate | |
| CN103182325B (en) | Catalyst, its preparation method and use its prepare the method for aromatic carbonate from dialkyl carbonate | |
| CN102295563A (en) | Preparation method of trinexapac-ethyl | |
| CN112574067B (en) | Method for preparing high-purity m-xylylene diisocyanate without phosgene | |
| KR101610470B1 (en) | Method for Preparing Diureido Compounds | |
| CN112439428B (en) | Preparation method and application of solid acid catalyst | |
| JPS5822108B2 (en) | Method for producing aromatic diurethane | |
| CN109265344B (en) | Preparation method of diphenyl carbonate compound | |
| CN100464852C (en) | Organic stannum sulfonate catalyst for exchange reaction of methyl carbonate and phenol ester | |
| CN111185246B (en) | Titanium catalyst, preparation and application | |
| KR101827596B1 (en) | Tin compound, method for preparing the same and method for preparing aromatic carbonate from dialkyl carbonate using the same | |
| CN109265342B (en) | Preparation method of diphenyl carbonate compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |