CN103781756B - Preparation method by the nitro paraffin of gas phase nitration reaction - Google Patents

Preparation method by the nitro paraffin of gas phase nitration reaction Download PDF

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Publication number
CN103781756B
CN103781756B CN201280042884.6A CN201280042884A CN103781756B CN 103781756 B CN103781756 B CN 103781756B CN 201280042884 A CN201280042884 A CN 201280042884A CN 103781756 B CN103781756 B CN 103781756B
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catalyst
metal
preparation
nitro
tio
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CN103781756A (en
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高相吉
金桢珠
张泰善
金镇亿
卢奇润
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Korea Research Institute of Chemical Technology KRICT
Kumho Petrochemical Co Ltd
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Korea Research Institute of Chemical Technology KRICT
Korea Kumho Petrochemical Co Ltd
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Priority claimed from KR1020110081922A external-priority patent/KR101282734B1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J37/0201—Impregnation

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention is about by specific solid acid catalyst, the method that solid base catalyst or these mixture use as catalyst and make hydrocarbon compound react with gas phase nitro agent and prepare nitro paraffin with high yield, even if implementing gas phase nitration reaction with condition of normal pressure can also obtain nitro paraffin by the highest yield, it is possible not only to batch-type step, reaction can be made to carry out with continuous way step, thus high as payable production method value.

Description

Preparation method by the nitro paraffin of gas phase nitration reaction
[technical field]
The method that the present invention relates to use specific solid acid catalyst, solid base catalyst or these mixture as catalyst and make hydrocarbon compound react with gas phase nitro agent and prepare nitro paraffin with high yield.
[background technology]
Nitro paraffin is that hydro carbons combines nitro (-NO2) the general name of compound, all the time at coating industrial field as the substance migration providing character to improve.Nitro paraffin is at synthesis material, reaction intermediate, separating step solvent, chemical stabilizer, fuel additive at present, uses with various purposes from the application replacing the high additive values such as water of metal surface.
Generally know that as the preparation method of nitro paraffin and make hydrocarbon compound and nitrous acid (NO2) the gas method that carries out nitration reaction and prepare.Such nitro paraffin preparation process is owing to carrying out under the condition of high voltage of the hot conditions of 50～800 DEG C of scopes and 70～110atm scopes, so danger is big, has limitation for being suitable for consecutive steps.It addition, the high pressure reaction assembly equipment used for maintaining condition of high voltage has shortcoming costly.The preparation method of the nitro paraffin disclosed in International Patent Publication WO2009/129099 is also to carry out nitration reaction with high temperature and condition of high voltage, and having need to be with the shortcoming of batch reactions restrictively administration step not being successive reaction.
To this, the present inventor prepares the method for nitro paraffin and has carried out several years research effort for improving conventional execution gas phase nitration reaction under high temperature and condition of high voltage.Its result finds out the reaction condition at milder also can implement new solid acid catalyst or the solid base catalyst on gas phase nitration reaction ground flexibly, thus completes the present invention.
[summary of the invention]
[inventing technical task to be solved]
It is desirable to provide specific solid acid catalyst, solid base catalyst or these mixture are used as catalyst and the method for preparing nitro paraffin with high yield under low pressure condition near normal pressure.
[solving the technical scheme of problem]
For solving described problem, the present invention reacts in the nitro agent of the hydrocarbon compound with gas phase that make carbon number 1～40 and prepares in the method for nitro paraffin, it is characterised in that use as described nitration reaction catalyst:
A () is selected from the solid acid catalyst of following more than a kind: the heteropoly acid shown in chemical formula 1 shown below；Selected from TiO2-Al2O3, TiO2-ZrO2, TiO2-ZnO, TiO2-MoO3, TiO2-La2O3And TiO2-WO3Metal composite oxide；And on described metal composite oxide, load the load fluorine metal composite oxide of fluorine anion (F-)；Or
B () is selected from the solid base catalyst of following more than a kind: comprise the metal-oxide of the metal of in Ca, Mg and Zn more than a kind；And the metal-oxide of the metal of more than comprise in Ca, Mg and Zn a kind is made as holder its load metal-oxide helping activated metal loading in K, Mg and Cr more than a kind；
Solid acid catalyst (a) described in (c) and the mixture of solid base catalyst (b).
［ chemical formula 1 ］
H11PM12-xO42-y
In described chemical formula 1, M is Mo5+, V2+, or its hybrid metal, x and y is to meet 0≤x≤12, the real number of 0≤y≤12 respectively.
As the embodiments of the present invention for solving described problem, it is characterised in that described solid acid catalyst (a) is selected from H3PMo12O40, and H11PMo6V6O42Heteropoly acid.
As the embodiments of the present invention for solving described problem, it is characterised in that described solid acid catalyst (a) is selected from TiO2-Al2O3, and TiO2-ZrO2Metal composite oxide.
As the embodiments of the present invention for solving described problem, it is characterised in that described solid acid catalyst (a) is selected from F-/TiO2-Al2O3, and F-/TiO2-ZrO2Load fluorine metal composite oxide.
As the embodiments of the present invention for solving described problem, it is characterised in that described solid base catalyst (b) is the metal-oxide selected from CaO, MgO, ZnO, CaMgO, CaZnO, MgZnO, and CaMgZnO.
As the embodiments of the present invention for solving described problem, it is characterised in that described solid base catalyst (b) is selected from K-CaO, Mg-CaO, Cr-CaO, K-MgO, Mg-MgO, Cr-MgO, K-ZnO, Mg-ZnO, Cr-CaMgO, K-CaMgO, Mg-CaMgO, Cr-CaMgO, Cr-CaMgO, K-CaZnO, Mg-CaZnO, Cr-CaZnO, K-MgZnO, Mg-MgZnO, the load metal-oxide of Cr-MgZnO, K-CaMgZnO, Mg-CaMgZnO and Cr-CaMgZnO.
[invention effect]
The nitro paraffin preparation method of the present invention is carried out with gas phase nitration reaction, implements can also obtain the effect of nitro paraffin by high yield even if nitration reaction has under the low pressure condition near normal pressure.
It addition, the nitro paraffin preparation method of the present invention is possible not only to batch-type step, it is also possible to continuous way step is carried out, so there being industry to utilize the effect that probability is big.
[embodiment]
The present invention relates to use specific solid acid catalyst, solid base catalyst or these mixture as catalyst and make hydrocarbon compound gas phase nitration reaction and the method for preparing nitro paraffin.
Solid acid catalyst and solid base catalyst for being applicable to the reaction system according to the present invention carries out being more particularly described as follows.
The solid acid catalyst used in the present invention is selected from: heteropoly acid, metal composite oxide, carries the metal composite oxide of fluorine, or these mixture.
The heteropoly acid used as solid acid catalyst in the present invention can represent with above-mentioned chemical formula 1.Heteropoly acid described in particular instantiation can comprise H3PMo12O40,H11PMo6V6O42Deng, these heteropoly acids can be used in mixed way.The preparation method of heteropoly acid represented by described chemical formula 1 is described briefly, then can be by phosphorus (P) precursor, molybdenum (Mo) precursor, in vanadium (V) precursor dispersion to distilled water after with 20～150 DEG C, preferably 90～100 DEG C temperature heating and prepare.It is more particularly described, then uses H as phosphorus precursor3PO4, use MoO as molybdenum precursor3, use V as vanadium precursor2O5, precursor described in mixing and be distributed to distilled water (H2O) dissolve in condition of heating after in and react and available H3PMo12O40Or H11PMo6V6O42Shown heteropoly acid.
The metal composite oxide used as solid acid catalyst in the present invention is with titanium dioxide (TiO2) as required composition, then co-precipitation is selected from aluminium oxide (Al2O3), zirconium oxide (ZrO2), zinc oxide (ZnO), molybdenum oxide (MoO3), lanthana (La2O3) and tungsten oxide (WO3) the metal composite oxide of metal-oxide of more than a kind.The preparation method of described metal composite oxide is described briefly, then by comprising titanium (Ti) precursor as required composition, then more than a kind can be co-precipitated is selected from aluminum (Al), zirconium (Zr), zinc (Zn), molybdenum (Mo), lanthanum (La), and the precursor of the metal of tungsten (W) and prepare.Described metal precursor is the metal-containing compound being suitable in this area routine, can use halogenide, hydroxide, oxide, C1～C6Alkoxide cpd, or the salt compound of organic or inorganic acid.Such as, titanium precursor can use selected from TiCl4, Ti [OCH (CH3)2]4, Ti (OC2H5)4, and Ti (SO4)2In more than a kind, aluminum precursor can use selected from Al (C2H3O2)3, AlCl3, Al (NO3)2, Al2(CO3)3, Al (OH)3And Al (C5H7O2)3In more than a kind, zirconium precursors can use selected from ZrCl4, Zr (NO3)4, ZrCO4, and Zr (OH)4In more than a kind, zinc precursor can use selected from ZnCl2, Zn (OAc)2, and Zn (NO3)2In more than a kind.Molybdenum precursor, lanthanum precursor, and tungsten precursor also can select to use in described category aptly.
The metal composite oxide carrying fluorine used as solid acid catalyst in the present invention can be by impregnating fluorine compounds such as to the metal composite oxide of above-mentioned preparation, CFCl3, HFCl4, or NH4After F, it is dried with 100 DEG C～150 DEG C of temperature, prepares with 250 DEG C～350 DEG C of temperature sintering.
The solid base catalyst used in the present invention can be metal-oxide, or loads the load metal-oxide helping activated metal of more than a kind using described metal-oxide as holder.
The metal-oxide used as solid base catalyst in the present invention is the material that the metal of more than a kind in Ca, Mg and Zn exists with oxide form, specifically selected from CaO, MgO, ZnO, CaMgO, CaZnO, MgZnO, and CaMgZnO.The preparation method of described metal-oxide is described briefly, then can be prepared for more than a kind by the precursor compound of the metal that mixing and sintering comprise Mg, Ca or Zn.Described metal precursor compound is the compound utilized in field of catalyst preparation routine, specifically can use the chloride of described metal, hydroxide, sulfide, nitrate, carbonate, sulfate, acetate etc..Specifically, metal precursor compound can comprise Mg (NO3)2·6H2O, MgCO3, MgCl2·6H2O, Mg (OH)2, Ca (NO3)2, Ca (NO2)2, CaCl2, CaCO3, Ca (OH)2, Zn (NO3)2·6H2O, Zn (NO3)2, ZnCO3, ZnCl2, Zn (OH)2Deng.Sintering temperature maintains 500 DEG C～1000 DEG C of scopes, and preferably 500 DEG C～900 DEG C of scopes, described sintering temperature is the lowest, then can have the problem that solid base catalyst does not generates, and too Gao Zeke has particle to be sintered and the problem of the activity decrease of catalyst.
In the case of the load metal oxide catalyst used as solid base catalyst in the present invention, the activated metal that helps loaded can more increase the basicity of catalyst surface, so more being strengthened the effect of the catalyst activity as solid base catalyst.It practice, can confirm that according to embodiments of the invention, comparing metal oxide catalyst, load helps the metal oxide catalyst that carries of activated metal to have the increase of catalyst activity of 3～about 7%.
The load metal-oxide used as solid base catalyst in the present invention specifically can comprise: K-CaO, Mg-CaO, Cr-CaO, K-MgO, Mg-MgO, Cr-MgO, K-ZnO, Mg-ZnO, Cr-CaMgO, K-CaMgO, Mg-CaMgO, Cr-CaMgO, Cr-CaMgO, K-CaZnO, Mg-CaZnO, Cr-CaZnO, K-MgZnO, Mg-MgZnO, Cr-MgZnO, K-CaMgZnO, Mg-CaMgZnO, Cr-CaMgZnO etc..
Loading the load metal-oxide helping activated metal of more than two kinds is of more than two kinds to help activated metal can be distributed equably in single coat, or helps activated metal can form different coats respectively and form multiple coat and be distributed.
nullThere is the load metal oxide catalyst helping activated metal mixed distribution of more than two kinds specifically can comprise at single coat: K,Mg-CaO，K,Cr-CaO，Mg,Cr-CaO，K,Mg,Cr-CaO，K,Mg-MgO，K,Cr-MgO，Mg,Cr-MgO，K,Mg,Cr-MgO，K,Mg-ZnO，K,Cr-ZnO，Mg,Cr-ZnO，K,Mg,Cr-ZnO，K,Mg-CaMgO，K,Cr-CaMgO，Mg,Cr-CaMgO，K,Mg,Cr-CaMgO，K,Mg-CaZnO，K,Cr-CaZnO，Mg,Cr-CaZnO，K,Mg,Cr-CaZnO，K,Cr-MgZnO，Mg,Cr-MgZnO，K,Mg,Cr-MgZnO，K,Cr-CaMgZnO，Mg,Cr-CaMgZnO，K,Mg,Cr-CaMgZnO etc..
Of more than two kinds help activated metal to coat individually and form multiple coat and there is the load metal oxide catalyst of core-shell structure copolymer (core-shell) structure and specifically can comprise K/Mg-CaO, Mg/K-CaO, K/Cr-CaO, Cr/K-CaO, Mg/Cr-CaO, Cr/Mg-CaO, K/Mg/Cr-CaO, K/Cr/Mg-CaO, Mg/K/Cr-CaO, Mg/Cr/K-CaO, Cr/K/Mg-CaO, Cr/Mg/K-CaO etc..Though wherein illustrating only CaO as metal oxide supports, but the metal-oxide used as holder in the present invention, use such as MgO, ZnO, CaMgO, CaZnO, MgZnO, or CaMgZnO, the metal oxide catalyst that carries with core-shell structure copolymer (core-shell) structure is also included in the interest field of the present invention.It addition, the present invention is without particular limitation for helping the load of activated metal and coating order to metal oxide supports load or coating.Additionally, mean using the CaO holder loading potassium (K) as core as carry ' the Cr/Mg/K-CaO catalyst ' that metal oxide catalyst illustrates with core-shell structure copolymer (core-shell) structure, successively coating magnesium (Mg) metal coat and chromium (Cr) metal coat and the load metal oxide catalyst of core-shell structure copolymer (core-shell) structure of coat in being formed.
The preparation method of the solid base catalyst carrying metal-oxide is the supported catalyst preparation method utilized in field of catalyst preparation routine, the available such as sedimentation method, load method, impregnation method etc..The solid base catalyst preparation method of representational load metal-oxide comprises following continuous print preparation process and carries out.Comprise such as, the precursor compound helping activated metal is dissolved in distilled water and prepares the process that helps activated metal precursor solution；Activated metal precursor solution is helped to add metal-oxide and the process of stirring of heating to described；And load helps the metal-oxide filtration drying of activated metal gather in the crops the process of load metal-oxide.Described help activated metal precursor compound be also field of catalyst preparation routine utilize compound, specifically can use the chloride of described metal, hydroxide, sulfide, nitrate, carbonate, sulfate, acetate etc..In the present invention, described help activated metal precursor solution preparation process can use more than a kind help activated metal precursor compound.It addition, activated metal loading process can be helped repeatedly to implement more than 2 times described continuous print.
It addition, solid acid catalyst described above, solid base catalyst or these mixture are used as catalyst and make hydrocarbon compound prepare nitro paraffin compound at gas phase condition nitration reaction by the present invention.
The hydrocarbon compound used in preparation in accordance with the present invention is the hydrocarbon compound of carbon number 1～40.Described hydrocarbon compound comprises whole straight chain type, and branching type is the most saturated, or the undersaturated hydrocarbon compound of part.Part unsaturated hydrocarbon compound refers to comprise the hydrocarbon compound of the double or triple bonds of more than 1.The hydrocarbon compound of gas phase of carbon number 1～4 is preferably used such as hydrocarbon compound, methane gas, ethane gas, propane gas, butane gas, compressed petroleum gas (LPG) etc..
And, make the nitro agent of described hydrocarbon compound nitration reaction can use nitrous acid (NO2), dinitrogen tetroxide (N2O4), nitric acid (HNO3) etc..
Nitrous acid (NO2) in the case of gas, by nitric acid and sulfur with 5～15:0.5～6 volume ratios, preferably for 8～10:2～4 volume ratio mixing, prepare in 150 DEG C of heating and use.In order to prevent moisture from entering nitrous acid (NO2) gas prepare inside reactor, cooling pit can be installed and remove moisture.Nitrous acid (the NO of preparation2) gas flows into inside reactor together with hydrocarbon compound and make to carry out gas phase nitration reaction, because of the density variation of hydrocarbon Yu nitrous acid gas, by hydrocarbon in the reactor and NO2What the uniformly mixing of gas and can expecting made nitro paraffin generates the effect that yield improves.
Nitration reaction under the solid acid catalyst according to the present invention near normal pressure under conditions of also can implement neatly.Specifically, nitration reaction be by hydrocarbon compound with nitro agent to become 1:0.5～30 volume ratios, for preferably, 1:10～20 volume ratios use, reaction pressure is near normal pressure, specifically maintain 0～1.5atm pressure limit, reaction temperature maintains 100～500 DEG C, preferably for the temperature range of 300～400 DEG C and implement nitration reaction 1～200 hours, preferably for 1～100 hour.
That is, the preparation method of conventional gas phase nitro paraffin need to maintain high pressure and hot conditions.But, the solid acid catalyst of motion of the present invention, solid base catalyst or these mixture are used as catalyst, even if then maintaining the most relatively low temperature can also prepare nitro paraffin by outstanding yield.Thus, the nitro paraffin preparation method of the present invention is possible not only to batch-type step, it is also possible to the advantage that continuous way step is carried out.
[embodiment]
The described above present invention is explained in more detail according to following preparation example and embodiment, the invention is not restricted to this.
The preparation of ［ preparation example ］ catalyst
[preparation example 1.H11PMo6V6O42The preparation of catalyst]
Mixing H3PO41.55g, MoO36.48g and V2O5It is scattered in water 200ml after 9.74g, and after 95 DEG C of dissolvings, evaporation, prepares H in 110 DEG C of the 2nd force dryings after drying in the rotary evaporator (rotary evaporator) maintaining 60 DEG C11PMo6V6O42Catalyst.
[preparation example 2.H11PMo12O40The preparation of catalyst]
Mixing H3PO4It is scattered in water 200ml after 1.55g and MoO312.96g, and after 95 DEG C of dissolvings, evaporation, prepares H in 110 DEG C of the 2nd force dryings after drying in the rotary evaporator (rotary evaporator) maintaining 60 DEG C11PMo12O40Catalyst.
[preparation example 3.TiO2-Al2O3The preparation of catalyst]
By TiCl424.89ml is dissolved in solution and the AlCl of frozen water 100ml32.87g is dissolved in the solution mixing of water 50ml.28%NH is dripped lentamente as precipitant3Solution and after being adjusted to pH8～9 and generating co-precipitation thing, its profit is washed with water 3 times, dried in the stove of 110 DEG C, sintering 3 hours the stoves of 480 DEG C (furnace) in and prepare TiO2-Al2O3Catalyst.
[preparation example 4.TiO2-ZrO2The preparation of catalyst]
By TiCl424.89ml is dissolved in solution and the ZrOCl of frozen water 100ml2·8H2O4.95g is dissolved in the solution mixing of water 50ml.28%NH is dripped lentamente as precipitant3Solution and after being adjusted to pH8～9 and generating co-precipitation thing, its profit is washed with water 3 times, dried in the stove of 110 DEG C, sintering 3 hours the stoves of 480 DEG C (furnace) in and prepare TiO2-ZrO2Catalyst.
[preparation example 5.TiO2The preparation of-ZnO catalyst]
By TiCl424.89ml is dissolved in solution and the ZnCl of frozen water 100ml214.8g is dissolved in the solution mixing of water 50ml.28%NH is dripped lentamente as precipitant3Solution and after being adjusted to pH8～9 and generating co-precipitation thing, its profit is washed with water 3 times, dried in the stove of 110 DEG C, sintering 3 hours the stoves of 480 DEG C (furnace) in and prepare TiO2-ZnO catalyst.
[preparation example 6.TiO2-MoO3The preparation of catalyst]
By TiCl424.89ml is dissolved in solution and the (NH of frozen water 100ml4)2·MoO412.3g is dissolved in the solution mixing of water 50ml.28%NH is dripped lentamente as precipitant3Solution and after being adjusted to pH8～9 and generating co-precipitation thing, its profit is washed with water 3 times, dried in the stove of 110 DEG C, sintering 3 hours the stoves of 480 DEG C (furnace) in and prepare TiO2-MoO3Catalyst.
[preparation example 7.TiO2-La2O3The preparation of catalyst]
By TiCl424.89ml is dissolved in solution and the La of frozen water 100ml2O3xH2O5.84g is dissolved in the solution mixing of water 50ml.28%NH is dripped lentamente as precipitant3Solution and after being adjusted to pH8～9 and generating co-precipitation thing, its profit is washed with water 3 times, dried in the stove of 110 DEG C, sintering 3 hours the stoves of 480 DEG C (furnace) in and prepare TiO2-La2O3Catalyst.
[preparation example 8.TiO2-WO3The preparation of catalyst]
By TiCl424.89ml is dissolved in solution and the WO of frozen water 100ml311.6g is dissolved in the solution mixing of water 50ml.28%NH is dripped lentamente as precipitant3Solution and after being adjusted to pH8～9 and generating co-precipitation thing, its profit is washed with water 3 times, dried in the stove of 110 DEG C, sintering 3 hours the stoves of 480 DEG C (furnace) in and prepare TiO2-WO3Catalyst.
[preparation of preparation example 9～14. load fluorine O composite metallic oxide catalyst]
By the respective metal-oxide 10%CFCl of preparation in described preparation example 4～83Solution processes, and dried in 120 DEG C, prepares load fluorine O composite metallic oxide catalyst in 300 DEG C of sintering in atmosphere.The load fluorine O composite metallic oxide catalyst of preparation is F-/TiO2-Al2O3Catalyst (preparation example 9), F-/TiO2-ZrO2Catalyst (preparation example 10), F-/TiO2-ZnO catalyst (preparation example 11), F-/TiO2-MoO3Catalyst (preparation example 12), F-/TiO2-La2O3Catalyst (preparation example 13), F-/TiO2-WO3Catalyst (preparation example 14).
[preparation of preparation example 15.MgO catalyst]
By Mg (NO3)2·6H2O prepares MgO catalyst in 600 DEG C of sintering 3 hours.
[preparation of preparation example 16.ZnO catalyst]
By Zn (NO3)2·6H2O33.84g is dissolved in H2After dripping the ammonia solution as precipitant (28～30%, SAMCHUN) after O150ml lentamente and being adjusted to pH8～9 and generate precipitate, utilize H2O washs 3 times, and dried in the stove of 110 DEG C, sinters 3 hours and prepare ZnO catalyst in the stove of 600 DEG C.
[preparation of preparation example 17.CaO catalyst]
By CaCl215.37g be dissolved in H2After dripping the ammonia solution as precipitant (28～30%, SAMCHUN) after O150ml lentamente and being adjusted to pH8～9 and generate precipitate, utilize H2O washs 3 times, and dried in the stove of 110 DEG C, sinters 3 hours and prepare CaO catalyst in the stove of 600 DEG C.
[preparation of preparation example 18.CaMgO catalyst]
By Mg (NO3)2·6H2O17.69g, CaCl27.69g be dissolved in H2After dripping the ammonia solution as precipitant (28～30%, SAMCHUN) after O150ml lentamente and being adjusted to pH8～9 and generate precipitate, utilize H2O washs 3 times, and dried in the stove of 110 DEG C, sinters 3 hours and prepare CaMgO catalyst in the stove of 600 DEG C.
[preparation of preparation example 19.CaZnO catalyst]
By Zn (NO3)2·6H2O16.92g, CaCl27.69g be dissolved in H2After dripping the ammonia solution as precipitant (28～30%, SAMCHUN) after O150ml lentamente and being adjusted to pH8～9 and generate precipitate, utilize H2O washs 3 times, and dried in the stove of 110 DEG C, sinters 3 hours and prepare CaZnO catalyst in the stove of 600 DEG C.
[preparation of preparation example 20.MgZnO catalyst]
By Zn (NO3)2·6H2O16.92g, Mg (NO3)2·6H2O17.69g is dissolved in H2After dripping the ammonia solution as precipitant (28～30%, SAMCHUN) after O150ml lentamente and being adjusted to pH8～9 and generate precipitate, utilize H2O washs 3 times, and dried in the stove of 110 DEG C, sinters 3 hours and prepare MgZnO catalyst in the stove of 600 DEG C.
[preparation of preparation example 21.Cr-CaO catalyst]
As the precursor of Cr by Cr (NO3)3·9H2After O3.85g is dissolved in distilled water 50ml, adds CaO holder 4.5g to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares the Cr-CaO catalyst of load C r on CaO holder.
[preparation of preparation example 22.Cr/K-CaO catalyst]
After KCl0.95g being dissolved in distilled water 50ml as the precursor of K, add CaO holder 4.5g to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2O washs after 3 times the stove in 100 DEG C and is dried and the K-CaO for preparing to load K on CaO holder.
Then, as the precursor of Cr by Cr (NO3)3·9H2After O3.85g is dissolved in distilled water 50ml, adds the K-CaO4.5g of above-mentioned preparation to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares and form the Cr/K-CaO catalyst of the nucleocapsid structure of potassium (K) coat using K-CaO as core (core), outer surface.
[preparation of preparation example 23.Cr/Mg-CaO catalyst]
As the precursor of Mg by Mg (NO3)2·6H2After O5.27g is dissolved in distilled water 50ml, adds CaO holder 4.5g to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2O washs after 3 times the stove in 100 DEG C and is dried and the Mg-CaO for preparing to load Mg on CaO holder.
Then, as the precursor of Cr by Cr (NO3)3·9H2After O3.85g is dissolved in distilled water 50ml, adds the Mg-CaO4.5g of above-mentioned preparation to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares and form the Cr/Mg-CaO catalyst of the nucleocapsid structure of chromium (Cr) coat using Mg-CaO as core (core), outer surface.
[preparation of preparation example 24.K/Cr-CaO catalyst]
As the precursor of Cr by Cr (NO3)3·9H2After O3.85g is dissolved in distilled water 50ml, adds CaO holder 4.5g to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares the Cr-CaO of load C r on CaO holder.
Then, after KCl0.95g being dissolved in distilled water 50ml as the precursor of K, add the Cr-CaO4.5g of above-mentioned preparation to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares and form the K/Cr-CaO catalyst of the nucleocapsid structure of potassium (K) coat using Cr-CaO as core (core), outer surface.
[preparation of preparation example 25.K/Cr-CaMgO catalyst]
As the precursor of Cr by Cr (NO3)3·9H2After O3.85g is dissolved in distilled water 50ml, adds CaMgO holder 4.5g to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares the Cr-CaMgO of load C r on CaMgO holder.
Then, as the precursor of K by KNO3After 1.61g is dissolved in distilled water 50ml, adds the Cr-CaMgO4.5g of above-mentioned preparation to this solution, and stir 3 hours in 70 DEG C.Then, described reactant is utilized H2The stove that O washs after 3 times in 100 DEG C is dried and prepares and form the K/Cr-CaMgO catalyst of the nucleocapsid structure of potassium (K) coat using Cr-CaMgO as core (core), outer surface.
The preparation of ［ embodiment ］ nitro paraffin
The synthesis of nitropropane of solid acid catalyst [embodiment 1～14. utilize]
For making nitrous acid (NO2) gas generation, put into nitric acid 1kg and sulfur 40g, utilize bar magnet to stir, and with 150 DEG C of temperature heating.The respective solid acid catalyst 0.2g of preparation in described preparation example 1～14, the nitrous acid (NO that will generate is filled to other reactor2) gas puts into reactor together with propane gas.Implement to test to 400 DEG C from 250 variations by reaction temperature to understand the yield of the nitro paraffin with reaction temperature.Reaction product uses gas chromatographic analysis.The results are shown in table 1 below.
［ table 1 ］
According to described embodiment 1～14, confirm when implementing the nitration reaction of propane under conditions of the solid acid catalyst using the present invention, the conversion ratio of the propane tendency that the conversion ratio of propane rises gradually along with temperature rising.Confirm that the yield of nitropropane shows the highest yield reaction temperature 325～375 DEG C, reaction temperature brings up to more than described temperature range, then instead the yield of nitropropane reduces.Generally, the reaction in the presence of the solid acid catalyst of embodiment 1～14 is compared with without catalysts conditions and is obtained the effect that yield significantly increases.It addition, carrying fluorine O composite metallic oxide catalyst is to load fluorine anion (F-) the most again, the confirmed yield rising when preparing nitro paraffin.
The synthesis of nitropropane of solid base catalyst [embodiment 15～25. utilize]
For making nitrous acid gas (NO2) generate, put into nitric acid 1kg and sulfur 40g, utilize bar magnet to stir, and with 150 DEG C of temperature heating.Fill in described preparation example 15～25 after the respective solid base catalyst 0.2g of preparation to other reactor, by the nitrous acid gas (NO of propane gas and above-mentioned generation2) put into reactor together.Implement to test to 400 DEG C from 250 DEG C of variations by reaction temperature for understanding the yield of the nitro paraffin with reaction temperature.Use gas to chromatograph for analyzing the reaction product obtained under the conditions of each reaction temperature, the results are shown in table 2 below.
［ table 2 ］
According to the result of described table 2, when implementing the nitration reaction of propane under conditions of the solid base catalyst using the present invention, confirm the tendency that the conversion ratio of propane rises gradually along with temperature rising.Generally, the reaction in the presence of the solid base catalyst of embodiment 15～25 is compared with without catalysts conditions, obtains the effect that yield significantly increases.
Using selected from CaO, the reaction (embodiment 15～17) of the solid base catalyst of the metal-oxide of MgO and ZnO confirms, when reaction temperature 325～375 DEG C, the yield of nitropropane is the highest, and reaction temperature brings up to more than described temperature range, then instead the yield of nitropropane reduces.It addition, using such as CaMgO, in the reaction (embodiment 17～20) of the solid base catalyst of the metal composite oxide of CaZnO, MgZnO, when reaction temperature 250～300 DEG C, the not only conversion ratio of propane, the yield of nitro compound is the highest.That is, compare the solid base catalyst of single metal-oxide, use the solid base catalyst of metal composite oxide can expect to reduce the effect of reaction temperature.
It addition, load such as K using to the holder of CaO metal-oxide, in the reaction (embodiment 21～25) of the solid base catalyst carrying metal-oxide helping activated metal of Mg, Cr, when 300 DEG C, the yield of nitropropane is the highest.Compare with the nitration reaction under CaO metal oxide catalyst (embodiment 17), the yield obtaining the highest about 400% in identical temperature conditions increases effect, even if reaction temperature to be reduced to about 250 DEG C, it is also possible to obtain nitro paraffin with the yield of embodiment 17 equity.Additionally, in the reaction (embodiment 25) using the K/Cr-CaMgO catalyst used by the metal composite oxide of CaMgO as holder, compare the K/Cr-CaO catalyst (embodiment 24) used by the single metal-oxide of CaO as holder, the not only conversion ratio of propane, also obtains the effect that the yield of nitro compound improves.Thus, combine the holder of metal-oxide aptly and help activated metal to constitute the solid base catalyst of the present invention, then using as nitro paraffin catalyst for preparing and outstanding activity can be expected.
[industrial applicibility]
As above observe, even if gas phase nitration reaction is implemented by the nitro paraffin preparation method in the presence of the solid acid catalyst of motion of the present invention or solid base catalyst in condition of normal pressure, it is also possible to the highest yield obtains nitro paraffin.Especially, the nitro paraffin preparation method of the present invention is possible not only to batch-type step, it is also possible to continuous way step makes reaction carry out, thus high as payable production method value.

Claims (4)

1. the preparation method of nitro paraffin, it is characterised in that in the hydrocarbonylation making carbon number 1～40 The nitro agent of compound and gas phase is reacted and is prepared in the method for nitro paraffin, as described nitro Agent uses nitrous acid gas, uses as nitration reaction catalyst:
A () is selected from the solid acid catalyst of following more than a kind: selected from TiO2-Al2O3, TiO2-ZrO2, TiO2-ZnO, TiO2-MoO3, TiO2-La2O3And TiO2-WO3Answer Close and on metal-oxide, load fluorine anion (F-) load fluorine metal composite oxide, or
B () is selected from the solid base catalyst of following more than a kind: will comprise selected from Ca, The metal-oxide of the metal of more than a kind in Mg and Zn makes it load choosing as holder The load metal-oxide helping activated metal of more than a kind in K, Mg and Cr, or
Solid acid catalyst (a) described in (c) and the mixture of solid base catalyst (b), And
Make to carry out gas phase nitro under the pressure of 0～1.5atm and the temperature conditions of 100～500 DEG C Change reaction and prepare, and
The load metal-oxide contained in wherein said solid base catalyst is selected from K-CaO, Mg-CaO, Cr-CaO, K-MgO, Mg-MgO, Cr-MgO, K-ZnO, Mg-ZnO, Cr-CaMgO, K-CaMgO, Mg-CaMgO, Cr-CaMgO, Cr-CaMgO, K-CaZnO, Mg-CaZnO, Cr-CaZnO, K-MgZnO, Mg-MgZnO, Cr-MgZnO, K-CaMgZnO, Mg-CaMgZnO, and Cr-CaMgZnO.
2. the preparation method of the nitro paraffin of claim 1, it is characterised in that described load fluorine is multiple Close the solid acid catalyst of metal-oxide selected from F-/TiO2-Al2O3, and F-/TiO2-ZrO2。
3. the preparation method of the nitro paraffin of claim 1 or 2, it is characterised in that nitration React and implement with continuous way step or batch-type step.
4. the preparation method of the nitro paraffin of claim 1 or 2, it is characterised in that hydrocarbonylation is closed Thing and nitro agent use with 1:5～30 volume range.
CN201280042884.6A 2011-08-17 2012-08-16 Preparation method by the nitro paraffin of gas phase nitration reaction Active CN103781756B (en)

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EP0134265A1 (en) * 1982-02-25 1985-03-20 The Dow Chemical Company Catalytic preparation of nitroalkanes from alkanes
US4551568A (en) * 1982-04-16 1985-11-05 Sumitomo Chemical Company, Limited Process for nitration of benzene

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JPS56169648A (en) * 1980-06-03 1981-12-26 Mitsui Toatsu Chem Inc Preparation of lower nitroparaffins
US4431842A (en) * 1982-12-01 1984-02-14 The Dow Chemical Company Catalytic preparation of nitroalkanes
KR101183822B1 (en) * 2009-12-18 2012-09-19 한국화학연구원 Preparing method of nitroparaffin using solid acidic catalyst

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US2905724A (en) * 1957-06-21 1959-09-22 Commercial Solvents Corp Process for vapor phase nitration of alkanes
EP0134265A1 (en) * 1982-02-25 1985-03-20 The Dow Chemical Company Catalytic preparation of nitroalkanes from alkanes
US4551568A (en) * 1982-04-16 1985-11-05 Sumitomo Chemical Company, Limited Process for nitration of benzene

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