CN101041623A - Method for preparation of (substituted radical containted) aminophenol by catalytic hydrogenation of (substituted radical containted) nitrophenol - Google Patents

Method for preparation of (substituted radical containted) aminophenol by catalytic hydrogenation of (substituted radical containted) nitrophenol Download PDF

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CN101041623A
CN101041623A CNA2007100400377A CN200710040037A CN101041623A CN 101041623 A CN101041623 A CN 101041623A CN A2007100400377 A CNA2007100400377 A CN A2007100400377A CN 200710040037 A CN200710040037 A CN 200710040037A CN 101041623 A CN101041623 A CN 101041623A
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reaction
containing substituent
nitrophenols
massfraction
catalyzer
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CN100554243C (en
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宁春利
张猛
张春雷
邵敬铭
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Shanghai Hua Yi new material Co., Ltd
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Shanghai Huayi Acrylic Acid Co Ltd
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Abstract

The invention discloses a making method of aminophenol with substituted group through hydrogenating nitrophenol with substituted group, which adopts Ni-A/X typed loaded catalyst, wherein A is one of Co, Mn, Cu, Cr, Mo, Ca, Zn, Fe and W; the carrier X is one of their composition of zeolite molecular sieve, Al2O3, SiO2, TiO2, MgO, active charcoal or amorphic aluminium silicate; the mass percentage of Ni in the catalyst is 2-45% and the mass percentage of component A is 1-40%.

Description

The method of a kind of (containing substituent) nitrophenols shortening preparation (containing substituent) amino-phenol
Technical field
The present invention relates to the method for a kind of (containing substituent) nitrophenols shortening preparation (containing substituent) amino-phenol, specifically, the present invention provides the catalyzer and the catalytic reaction method thereof of synthetic (the containing substituent) amino-phenol of nitrophenols hydrogenation of a kind of being used for (containing substituent).
Background technology
The amino-phenol compounds of amino-phenol and replacement has the wide industrial purposes, is a class important chemical product or an intermediate, can be used for many fields such as dyestuff, rubber, medicine, agricultural chemicals, weaving.P-aminophenol for example, Ortho-Aminophenol, Metha Amino Phenon can be used for synthetic medicine, dyestuff, sensitive materials, hair dye, oil product oxidation inhibitor, multiple fine chemicals such as rubber ingredients and intermediate, 2-methyl-5-amino-phenol can be used as the intermediate of hair dye, 2-oxyethyl group-4-amino-phenol is a kind of broad-spectrum medicine intermediate, 2-amino-4-methylphenol is used to produce dyestuff and white dyes DT etc., 4-amino-2, the 6-diaminophenol is an intermediate of producing sterilant fluorine bell urea, and 4-amino-3-methylphenol is to produce dyestuff, the intermediate of fine chemicals such as agricultural chemicals.
The production method of the amino-phenol compounds of amino-phenol and replacement mainly contains the oil of mirbane electrolytic reduction of shortening method, oil of mirbane and the replacement of oil of mirbane in acidic solution of nitrophenols iron powder reducing method, oil of mirbane and the replacement of nitrophenols and replacement.The example that synthesizes with p-aminophenol, the method that a kind of iron powder reducing legal system is equipped with p-aminophenol has been described among the Chinese patent CN1562959, about 90～100 ℃, p-NP added to contain and carry out reduction reaction in iron powder and the aqueous solution of hydrochloric acid, reaction finishes back elimination iron mud, add Sodium Pyrosulfite in the mother liquor, be cooled to again about 55 ℃, obtain finished product through aftertreatments such as recrystallization, dryings.Though this method process is simple, the production cost height, environmental pollution is serious, and product purity is low, and product can only be used for dyestuff, and can not be directly used in pharmaceutical industries.The patent report of oil of mirbane shortening method is a lot of, as U.S. Pat P3654365, USP3715397, USP4885389, USP4307249, Chinese patent CN1167108, CN1562465, CN1285407 etc., Pt/C, Pd/C and the corresponding oxide compounds thereof of adopting are made catalyzer more in the technology of these patent reports, hydrogenation is rearranged into p-aminophenol with nitrobenzene reduction behind the generation intermediate product azanol again in acidic medium.The synthetic method that the oil of mirbane electrolytic reduction prepares p-aminophenol has been described among the Chinese patent CN1061808.Reported with the p-NP to be the method for feedstock production p-aminophenol among the Chinese patent CN1377875,1207267,1257150, the catalyzer that adopts in these patents is skeleton nickel, Pt/C, Pd/C or Ni/C etc.Because these catalyzer will use being broken under the very thin granularity, cause the catalyst recovery difficulty, and the expensive manufacturing cost of noble metal catalyst will reduce the economy of process undoubtedly.
Summary of the invention
The object of the present invention is to provide the effective catalyst and the catalytic hydrogenation method of a kind of (containing substituent) nitrophenols hydrogenation preparing (containing substituent) amino-phenol, this catalyzer is the Ni-A/X bi-component supported catalyst, be used for (containing substituent) nitrophenols hydrogenation preparing (containing substituent) amino-phenol reactive activity and selectivity height, the reaction conditions gentleness, drawbacks such as the serious and poor product quality of environmental pollution that patent CN1562959 as described above adopts the iron powder reducing method to cause have been overcome simultaneously effectively, solved USP3654365, patent such as CN1167108 and CN1377875 adopts problems such as expensive noble metal catalyst and catalyst recovery difficulty, and avoided the CN1061808 patent to adopt shortcomings such as electrolytic reduction process energy consumption is high, for preparation (containing substituent) amino-phenol provides a kind of novel method.
The present invention is achieved by the following technical solutions:
A kind of molecular structure (containing substituent) nitrophenols shortening shown in (I) prepares the method for molecular structure (containing substituent) amino-phenol shown in (II), the catalyzer that adopts is the Ni-A/X loaded catalyst, wherein component A is any among Ca, Co, Mn, Cu, Cr, Zn, Fe, Mo, W, B, Ti, the V, preferred Co, Mn, Cu, Cr, Mo, Ca, Zn, Fe; Carrier X is zeolite molecular sieve, Al 2O 3, SiO 2, TiO 2, any or they in MgO, gac or the amorphous aluminum silicate mixture, preferred γ-Al 2O 3, SiO 2, amorphous aluminum silicate or h-type zeolite molecular sieve ZSM-5, MCM-22, MCM-49, SAPO-34, mordenite, Y zeolite, β zeolite; The massfraction of Ni is 2～45% in the catalyzer, is preferably 5～35%; The massfraction of component A is 1～40%, is preferably 5～30%.
Figure A20071004003700061
In (containing substituent) nitrophenols or (containing substituent) amino-phenol molecular structure, R1～R5 is hydrogen or chlorine, bromine, fluorine, hydroxyl, amino, nitro, contain the alkyl of 1 to 4 carbon atom, contain a kind of in the alkoxyl group of 1 to 4 carbon atom, R1, R2, R3, R4 and R5 are identical substituting group or different substituting groups, but have at least one to be hydroxyl among R1～R5.
The Ni-A/X loaded catalyst is by pickling process or hybrid system preparation.It is presoma with support powder and active ingredient that hybrid system prepares catalyzer, mixes and extrusion or compression molding by certain metering ratio as soluble salt or metal oxide etc., becomes the metal oxide form in dry, roasting then.The immersion process for preparing catalyzer be be mixed with the certain density soluble salts of active components aqueous solution according to certain metering than flooding in the support of the catalyst that adds moulding in advance, dry then, roasting becomes the metal oxide form.Need with hydrogen the loaded catalyst for preparing to be carried out reduction activation before use and handle, reductive condition is hydrogen pressure 0.2～10.0MPa, hydrogen gas space velocity 100～1500h -1, 250～650 ℃ of reduction temperatures, 1～48 hour recovery time, preferred hydrogen pressure 2.0～8.0MPa, hydrogen gas space velocity 300～1000h -1, 300～500 ℃ of reduction temperatures, 4～20 hours recovery times.
The reaction of (containing substituent) nitrophenols shortening preparation (containing substituent) amino-phenol both can be adopted still reaction, also can adopt fixed bed reaction.The still reaction condition is 2～15% for (containing substituent) nitrophenols massfraction, preferred 6～12%; Solvent for use is water, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, phenylcarbinol, ether, acetonitrile, chloroform, tetracol phenixin, benzene or toluene, preferably water, ethanol or Virahol; The catalyzer add-on is 0.5～10% of a reaction system quality, preferred 1～6%; 40～200 ℃ of temperature of reaction, preferred 60～140 ℃; Reaction pressure 0.2～15.0MPa, preferred 2.0～10.0MPa; 2～24 hours reaction times, preferred 4～8 hours.The fixed bed reaction condition is 2～10% for (containing substituent) nitrophenols massfraction, preferred 3～6%; Solvent for use is water, ethanol, Virahol, propyl carbinol or ether, preferably water, ethanol or Virahol; 40～200 ℃ of temperature of reaction, preferred 50～150 ℃; Reaction pressure 0.5～15.0MPa, preferred 2.0～8.0MPa; (containing substituent), nitrophenols solution air speed was 0.5～15.0h -1, preferred 2.0～10.0h -1H 2/ (containing substituent), the nitrophenols mol ratio was 2: 1～25: 1, preferred 5: 1～10: 1.
Embodiment
To be illustrated with specific embodiment below, but content of the present invention is not limited to these embodiment.
Embodiment 1～19
Preparation of catalysts:
Hybrid system prepares catalyzer with the solubility salt aqueous solution of certain density nickel nitrate aqueous solution and component A or the oxide compound of A, add in the support of the catalyst according to certain metering ratio, mix and extrusion or compression molding, then 120 ℃ dry 20 hours down, 600 ℃ of following roastings 4 hours.Reduce to room temperature after roasting finishes, in the reactor of packing into, 450 ℃ with hydrogen reducing 4 hours, after reduction finishes condition is adjusted to the required condition of reaction.The composition of catalyzer among each embodiment, the starting material kind of component A sees Table 1.
The catalyzer of table 1 hybrid system preparation is formed
Embodiment Component A The starting material of component A Carrier X The quality percentage composition of Ni, % The quality percentage composition of A, %
Embodiment 1 Co Xiao Suangu γ-Al 2O 3 22 5
Embodiment 2 Mn Manganous nitrate SiO 2 19 15
Embodiment 3 Cu Cupric nitrate Amorphous silicon aluminium 24 10
Embodiment 4 Cr Chromium nitrate The HZSM-5 molecular sieve 21 12
Embodiment 5 Cr Chromic oxide The SAPO-34 molecular sieve 33 15
Embodiment 6 Ca Nitrocalcite The HY molecular sieve 18 15
Embodiment 7 Ca Calcium oxide The H beta-molecular sieve 31 20
Embodiment 8 Zn Zinc nitrate The HMCM-49 molecular sieve 20 14
Embodiment 9 Mo Ammonium molybdate Mordenite molecular sieve 20 6
Embodiment 10 Mo Molybdenum oxide The H beta-molecular sieve 25 15
Embodiment 11 Fe Iron nitrate The MCM-22 molecular sieve 20 28
The solubility salt aqueous solution of certain density nickel nitrate aqueous solution of immersion process for preparing catalyst preparation and component A floods than adding in the support of the catalyst according to certain metering, then 110 ℃ dry 12 hours down, 550 ℃ of following roastings 6 hours.Reduce to room temperature after roasting finishes, in the reactor of packing into, 480 ℃ with hydrogen reducing 4 hours, after reduction finishes condition is adjusted to the required condition of reaction.The composition of catalyzer among each embodiment, the starting material kind of component A sees Table 2.
Table 2 catalyst prepared is formed
Embodiment Component A The starting material of component A Carrier X The weight percentage of Ni, % The weight percentage of A, %
Embodiment 12 Co Xiao Suangu Al 2O 3 25 6
Embodiment 13 Mn Manganous nitrate SiO 2 16 12
Embodiment 14 Cu Cupric nitrate Amorphous silicon aluminium 28 12
Embodiment 15 Cr Chromium nitrate Mordenite molecular sieve 35 10
Embodiment 16 Ca Nitrocalcite The HY molecular sieve 26 12
Embodiment 17 Zn Zinc nitrate The HMCM49 molecular sieve 30 14
Embodiment 18 Mo Ammonium molybdate Mordenite molecular sieve 30 10
Embodiment 19 Fe Iron nitrate The MCM22 molecular sieve 30 27
The reactive behavior evaluation of catalyzer:
Intermittently still reaction is respectively charged into the catalyzer among the embodiment 1～8 of metering in the tubular reactor; reduce to room temperature with hydrogen reducing after 4 hours for 450 ℃; under nitrogen protection, be transferred to then in 500 milliliters of stainless steel high pressure stirred autoclaves; add 280 gram water or alcohol solvent, 20 gram (containing substituent) nitrophenols raw materials more respectively; be warming up to 80 ℃ and feed hydrogen after the sealing; control reaction pressure 0.1～10MPa, 80～180 ℃ of temperature of reaction, stirring velocity 500～2000 are changeed, and it is zero reacting to hydrogen flowing quantity.Reaction conditions and reaction result concrete among the embodiment 1～8 see Table 3.
Table 3 batch still formula reaction conditions and result
Embodiment Reaction raw materials Solvent Temperature of reaction, ℃ Reaction pressure, MPa The catalyzer add-on, % (quality) Transformation efficiency, % Selectivity, %
Embodiment 1 P-NP Water 90 2.0 2.0 100 99.5
Embodiment 2 O-NP Water 85 2.0 3.0 100 99.2
Embodiment 3 M-nitrophenol Ethanol 80 3.0 3.0 98.3 99.1
Embodiment 4 Between the methyl p-NP Ethanol 95 5.0 3.0 95.5 99.5
Embodiment 5 Adjacent methyl p-NP Ethanol 95 5.0 4.0 97.2 98.5
Embodiment 6 To the tert-butyl o nitrophenols Ethanol 110 5.0 3.0 97.2 99.5
Embodiment 7 Adjacent chlorine p-NP Water 100 5.0 5.0 95.6 99.2
Embodiment 8 Adjacent fluorine p-NP Ethanol 100 5.0 3.0 95 99.8
Continuous fixed bed reaction or continuous is respectively charged into the catalyzer among the embodiment 9～19 100 gram in the fixed-bed tube reactor, and 450 ℃ with hydrogen reducing 4 hours, and reduction cools the temperature to temperature of reaction after finishing.Massfraction is to enter reactor reaction after 6% raw material and the hydrogen mixing preheating.Reaction conditions and reaction result concrete among the embodiment 9～19 see Table 4.
Table 4 continuous fixed bed reaction or continuous condition and result
Embodiment Reaction raw materials Solvent Temperature of reaction, ℃ Reaction pressure, MPa Air speed, h -1 Transformation efficiency, % Selectivity, %
Embodiment 9 P-NP Water 110 5.0 4.0 100 99.8
Embodiment 10 To the methyl o-NP Water 120 4.0 3.0 100 98.5
Embodiment 11 Between the methyl p-NP Ethanol 100 3.0 4.5 100 99.5
Embodiment 12 To the methoxyl group o-NP Ethanol 100 5.0 4.0 99.5 99.2
Embodiment 13 Between the ethyl p-NP Ethanol 110 5.0 4.0 98.5 99.3
Embodiment 14 To the tert-butyl o nitrophenols Ethanol 120 4.0 3.5 100 99.2
Embodiment 15 To the methyl o-NP Water 120 5.0 3.0 100 99.4
Embodiment 16 To the methyl o-NP Ethanol 130 3.0 2.0 100 99.5
Embodiment 17 Between the ethyl p-NP Ethanol 100 5.0 1.5 100 99.3
Embodiment 18 Between the ethyl p-NP Water 120 5.0 1.0 100 99.5
Embodiment 19 To the tert-butyl o nitrophenols Ethanol 100 5.0 1.0 100 99.5
Embodiment 20～28
With the catalyzer among the embodiment 15 100 gram fixed-bed tube reactor of packing into, 450 ℃ with hydrogen reducing 4 hours, and reduction cools the temperature to temperature of reaction after finishing.Massfraction is to enter reactor reaction after 6% p-NP and the hydrogen mixing preheating, and reaction conditions and reaction result concrete among the embodiment 20～28 see Table 5.
Table 5.
Embodiment Solvent Temperature of reaction, ℃ Reaction pressure, MPa Air speed, h -1 Transformation efficiency, % Selectivity, %
Embodiment 20 Water 50 5.0 2.0 85 99
Embodiment 21 Water 60 5.0 2.0 98 99.2
Embodiment 22 Water 80 5.0 2.0 100 99.6
Embodiment 23 Water 100 5.0 2.0 100 99.5
Embodiment 24 Water 120 5.0 2.0 100 99.3
Embodiment 25 Water 100 5.0 1.0 100 99.2
Embodiment 26 Water 100 5.0 3.0 100 99.7
Embodiment 27 Water 100 5.0 4.0 100 98.5
Embodiment 28 Water 100 5.0 6.0 100 99.1

Claims (6)

1, the method for a kind of (containing substituent) nitrophenols shortening preparation (containing substituent) amino-phenol is characterized in that:
A) described (containing substituent), nitrophenols had the molecular structure shown in (I), and (containing substituent), amino-phenol had the molecular structure shown in (II):
Figure A2007100400370002C1
Wherein, R1～R5 is hydrogen or chlorine, bromine, fluorine, hydroxyl, amino, nitro, contain the alkyl of 1～4 carbon atom, contain a kind of in the alkoxyl group of 1～4 carbon atom, and R1, R2, R3, R4 or R5 are identical substituting group or different substituting groups, but have at least one to be hydroxyl among R1～R5;
B) catalyzer of this method employing is the Ni-A/X loaded catalyst, and wherein component A is any among Ca, Co, Mn, Cu, Cr, Zn, Fe, Mo, W, B, Ti, the V, and carrier X is zeolite molecular sieve, Al 2O 3, SiO 2, TiO 2, any or they in MgO, gac or the amorphous aluminum silicate mixture, the massfraction of Ni is 2～45% in the catalyzer, the massfraction of component A is 1～40%;
C) reactive mode of this method employing is still reaction or fixed bed reaction.
2, method according to claim 1, it is characterized in that component A in the loaded catalyst is any among Ca, Co, Mn, Cu, Cr, Zn, Fe, the Mo, carrier X is any in h-type zeolite molecular sieve ZSM-5, MCM-22, MCM-49, SAPO-34, mordenite, Y zeolite or the β zeolite, perhaps γ-Al 2O 3, SiO 2, or amorphous aluminum silicate in any, the massfraction of component Ni is 5～35%, the massfraction of component A is 5～30%.
3, method according to claim 1 and 2 is characterized in that catalyzer adopts pickling process or hybrid system preparation, and needs to reduce processing before use that in hydrogen reductive condition is hydrogen pressure 0.2～10.0MPa, hydrogen gas space velocity 100～1500h -1, 250～650 ℃ of reduction temperatures, 1～48 hour recovery time.
4, method according to claim 3, the reductive condition that it is characterized in that catalyzer are hydrogen pressure 2.0～8.0MPa, hydrogen gas space velocity 300～1000h -1, 300～500 ℃ of reduction temperatures, 4～20 hours recovery times.
5, method according to claim 1, it is characterized in that the still reaction condition is 2～15% for (containing substituent) nitrophenols massfraction, solvent for use is water, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, phenylcarbinol, ether, acetonitrile, chloroform, tetracol phenixin, benzene or toluene, the catalyzer add-on is 0.5～10% of a reaction system quality, 40～200 ℃ of temperature of reaction, reaction pressure 0.2～15.0MPa, 2～24 hours reaction times; The fixed bed reaction condition is 2～10% for (containing substituent) nitrophenols massfraction, solvent for use is water, ethanol, Virahol, propyl carbinol or ether, 40～200 ℃ of temperature of reaction, reaction pressure 0.5～15.0MPa, (containing substituent), nitrophenols solution air speed was 0.5～15.0h -1, H 2/ (containing substituent), the mol ratio of nitrophenols was 2: 1～25: 1.
6, method according to claim 5, it is characterized in that the still reaction condition is 6～12% for (containing substituent) nitrophenols massfraction, solvent for use is water, ethanol or Virahol, the catalyzer add-on is 1～6% of a reaction system quality, 60～140 ℃ of temperature of reaction, reaction pressure 2.0～10.0MPa, 4～8 hours reaction times; The fixed bed reaction condition is 3～6% for (containing substituent) nitrophenols massfraction, solvent for use is water, ethanol or Virahol, 50～150 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa, (containing substituent), nitrophenols solution air speed was 2.0～10.0h -1, H 2/ (containing substituent), the mol ratio of nitrophenols was 5: 1～10: 1.
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