CN103781756A - Method for preparing nitroparaffin by gas phase nitration - Google Patents

Method for preparing nitroparaffin by gas phase nitration Download PDF

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Publication number
CN103781756A
CN103781756A CN201280042884.6A CN201280042884A CN103781756A CN 103781756 A CN103781756 A CN 103781756A CN 201280042884 A CN201280042884 A CN 201280042884A CN 103781756 A CN103781756 A CN 103781756A
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preparation
tio
nitro
cao
camgo
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CN103781756B (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
Priority claimed from KR1020110081923A external-priority patent/KR101282735B1/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

Abstract

The present invention relates to a method for preparing nitroparaffin in high yield by reacting a hydrocarbon compound and a gas phase nitration agent by using a specific solid acid catalyst, a solid base catalyst or a mixture thereof as a catalyst. The method can obtain a sufficiently high yield of nitroparaffin although the gas phase nitration is carried out in normal pressure conditions, and carry out the reaction through a continuous process as well as a batch-type process, such that the method is very useful as an industrial production method.

Description

By the preparation method of the nitro paraffin of gas phase nitration reaction
[technical field]
The present invention relates to specific solid acid catalyst, solid base catalyst or these mixture use as catalyzer and hydrocarbon compound is reacted with gas phase nitro agent and prepare the method for nitro paraffin with high yield.
[background technology]
Nitro paraffin is that hydro carbons is in conjunction with nitro (NO 2) the general name of compound, use as the material that provides character to improve applying industrial field all the time.At present nitro paraffin is at synthesis material, reaction intermediate, separating step solvent, chemical stabilizer, fuel dope, from the Application Areas of the high additive values such as the replacement water of metallic surface with various purposes use.
Generally know that and make hydrocarbon compound and nitrous acid (NO as the preparation method of nitro paraffin 2) gas carries out nitration reaction and the method prepared.Under the condition of high voltage of such nitro paraffin preparation process due to the hot conditions 50～800 ℃ of scopes and 70～110atm scope, carry out, thus dangerous large, for being suitable for and having limitation with consecutive steps.In addition, have for maintaining the high pressure reaction assembly equipment that condition of high voltage uses the shortcoming that expense is high.In No. WO2009/129099, International Patent Publication, the preparation method of disclosed nitro paraffin carries out nitration reaction with high temperature and condition of high voltage, and having need be not to be the restrictively shortcoming of administration step of batch reactions of successive reaction.
To this, the inventor prepares the method for nitro paraffin and has carried out several years research effort for the gas phase nitration reaction of implementing under high temperature and condition of high voltage improving in the past.Its result is found out new solid acid catalyst or the solid base catalyst that also can implement flexibly gas phase nitration reaction ground at the reaction conditions of milder, thereby completes the present invention.
[summary of the invention]
[technical task that invention will solve]
The present invention aims to provide specific solid acid catalyst, and solid base catalyst or these mixture are prepared the method for nitro paraffin under near low pressure condition normal pressure with high yield as catalyzer use.
[solving the technical scheme of problem]
For solving described problem, the present invention, making the hydrocarbon compound of carbonatoms 1～40 and the nitro agent of gas phase react and prepare in the method for nitro paraffin, is characterized in that, uses as described nitration reaction catalyzer:
(a) be selected from following a kind of above solid acid catalyst: under show the heteropolyacid shown in Chemical formula 1; Be selected from TiO 2-Al 2o 3, TiO 2-ZrO 2, TiO 2-ZnO, TiO 2-MoO 3, TiO 2-La 2o 3and TiO 2-WO 3complex metal oxides; And on described complex metal oxides load fluorine anion (F-) carry fluorine complex metal oxides; Or
(b) be selected from a kind of following above solid base catalyst: the metal oxide that comprises the a kind of above metal being selected from Ca, Mg and Zn; And make its load be selected from K as upholder the metal oxide that comprises the a kind of above metal being selected from Ca, Mg and Zn, a kind of above metal oxide that carries that helps activated metal in Mg and Cr;
(c) described solid acid catalyst (a) and the mixture of solid base catalyst (b).
［ Chemical formula 1 ］
H 11PM 12-xO 42-y
In described Chemical formula 1, M is Mo 5+, V 2+, or its hybrid metal, x and y meet 0≤x≤12, the real number of 0≤y≤12.
As for solve described problem of the present invention-embodiment, it is characterized in that, described solid acid catalyst (a) is selected from H 3pMo 12o 40, and H 11pMo 6v 6o 42heteropolyacid.
As for solve described problem of the present invention-embodiment, it is characterized in that, described solid acid catalyst (a) is selected from TiO 2-Al 2o 3, and TiO 2-ZrO 2complex metal oxides.
As for solve described problem of the present invention-embodiment, it is characterized in that, described solid acid catalyst (a) is selected from F-/TiO 2-Al 2o 3, and F-/TiO 2-ZrO 2carry fluorine complex metal oxides.
As for solve described problem of the present invention-embodiment, it is characterized in that, described solid base catalyst (b) is to be selected from CaO, MgO, ZnO, CaMgO, CaZnO, MgZnO, and the metal oxide of CaMgZnO.
As for solve described problem of the present invention-embodiment, it is characterized in that, described solid base catalyst (b) is to be 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, year metal oxide of Mg-CaMgZnO and Cr-CaMgZnO.
[invention effect]
Nitro paraffin preparation method of the present invention carries out with gas phase nitration reaction, implements also even if nitration reaction has under near the low pressure condition normal pressure effect that can high yield obtains nitro paraffin.
In addition, nitro paraffin preparation method of the present invention not only can batch-type step, can also continous way step carry out, so there is industry to utilize the effect that possibility is large.
[embodiment]
The present invention relates to specific solid acid catalyst, solid base catalyst or these mixture use as catalyzer and make hydrocarbon compound gas phase nitration reaction and prepare the method for nitro paraffin.
More specifically illustrate as follows for being applicable to according to the solid acid catalyst of reaction system of the present invention and solid base catalyst.
The solid acid catalyst using in the present invention is selected from: heteropolyacid, complex metal oxides, the complex metal oxides of year fluorine, or these mixture.
The heteropolyacid using as solid acid catalyst in the present invention can represent with above-mentioned Chemical formula 1.Described in particular instantiation, heteropolyacid can comprise H 3pMo 12o 40, H 11pMo 6v 6o 42deng, these heteropolyacids can mix use.The preparation method of the represented heteropolyacid of described Chemical formula 1 is described briefly, can be by phosphorus (P) precursor, molybdenum (Mo) precursor, after vanadium (V) precursor is distributed in distilled water, with 20～150 ℃, preferably 90～100 ℃ of temperature heat and prepare.More specifically explanation, is used H as phosphorus precursor 3pO 4, use MoO as molybdenum precursor 3, use V as vanadium precursor 2o 5, mix described precursor and be distributed to distilled water (H 2o) after in, can obtain H in heating condition dissolving and reaction 3pMo 12o 40or H 11pMo 6v 6o 42shown heteropolyacid.
The complex metal oxides using as solid acid catalyst is in the present invention with titanium dioxide (TiO 2) as essential composition, then co-precipitation is selected from aluminum oxide (Al 2o 3), zirconium white (ZrO 2), zinc oxide (ZnO), molybdenum oxide (MoO 3), lanthanum trioxide (La 2o 3) and Tungsten oxide 99.999 (WO 3) the complex metal oxides of a kind of above metal oxide.The preparation method of the described complex metal oxides of explanation briefly, can be by comprising titanium (Ti) precursor as essential composition, then a kind of co-precipitation is selected from aluminium (Al) above, zirconium (Zr), zinc (Zn), molybdenum (Mo), lanthanum (La), and the precursor of the metal of tungsten (W) and preparing.Described metal precursor is the metal-containing compound conventional applicable in this area, can use halogenide, oxyhydroxide, oxide compound, C 1～C 6alkoxide cpd, or the salt compound of organic or inorganic acid.For example, titanium precursor can use and be selected from TiCl 4, Ti[OCH (CH 3) 2] 4, Ti (OC 2h 5) 4, and Ti (SO 4) 2in more than a kind, aluminum precursor can use and be selected from Al (C 2h 3o 2) 3, AlCl 3, Al (NO 3) 2, Al 2(CO 3) 3, Al (OH) 3and Al (C 5h 7o 2) 3in more than a kind, zirconium precursors can use and be selected from ZrCl 4, Zr (NO 3) 4, ZrCO 4, and Zr (OH) 4in more than a kind, zinc precursor can use and be selected from ZnCl 2, Zn (OAc) 2, and Zn (NO 3) 2in more than a kind.Molybdenum precursor, lanthanum precursor, and tungsten precursor also can be in described category choice for use aptly.
The complex metal oxides that carries fluorine using as solid acid catalyst in the present invention can be by the complex metal oxides dipping fluorine cpd to above-mentioned preparation for example, CFCl 3, HFCl 4, or NH 4after F, dry with 100 ℃～150 ℃ temperature, prepare with 250 ℃～350 ℃ temperature sintering.
The solid base catalyst using in the present invention can be metal oxide, or using described metal oxide as upholder and load more than a kind help activated metal carry metal oxide.
The metal oxide using as solid base catalyst is in the present invention the a kind of material that above metal exists with oxide form being selected from Ca, Mg and Zn, is particularly selected from CaO, MgO, ZnO, CaMgO, CaZnO, MgZnO, and CaMgZnO.The preparation method of the described metal oxide of explanation briefly, can be by mixing and sintering comprise Mg, a kind of the precursor compound of the metal of Ca or Zn with on prepare.Described metal precursor compound is at the conventional compound utilizing of catalyzer preparation field, particularly can use the muriate of described metal, oxyhydroxide, sulfide, nitrate, carbonate, vitriol, acetate etc.Particularly, metal precursor compound can comprise Mg (NO 3) 26H 2o, MgCO 3, MgCl 26H 2o, Mg (OH) 2, Ca (NO 3) 2, Ca (NO 2) 2, CaCl 2, CaCO 3, Ca (OH) 2, Zn (NO 3) 26H 2o, Zn (NO 3) 2, ZnCO 3, ZnCl 2, Zn (OH) 2deng.Sintering temperature maintains 500 ℃～1000 ℃ scopes, and preferably, 500 ℃～900 ℃ scopes, described sintering temperature is too low, the problem that can have solid base catalyst not generate, and too Gao Zeke has particle to be sintered and problem that the activity of catalyzer declines.
In the situation of carrying metal oxide catalyst using as solid base catalyst in the present invention, can more increase the basicity of catalyst surface by the activated metal that helps of load, so can obtain more strengthening the effect as the catalyst activity of solid base catalyst.In fact, can confirm according to embodiments of the invention, compare metal oxide catalyst, load helps year metal oxide catalyst of activated metal to have the increase of the catalyst activity of 3～7% left and right.
Year metal oxide using 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.
Load is of more than two kinds, and to help the metal oxide that carries of activated metal be that the activated metal that helps of more than two kinds can distribute equably in single coat, or help activated metal to form respectively different coats and form multiple coats and distribute.
There is a year metal oxide catalyst that helps 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 kindsly help indivedual coating of activated metal and form multiple coats and there is carrying a metal oxide catalyst and specifically can comprising K/Mg-CaO of core-shell (core-shell) structure, 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 illustrate only CaO as metal oxide upholder, but the metal oxide using as upholder in the present invention, use for example MgO, ZnO, CaMgO, CaZnO, MgZnO, or CaMgZnO, the metal oxide catalyst that carries with core-shell (core-shell) structure is also included in interest field of the present invention.In addition, the present invention is without particular limitation for the load that helps activated metal to the load of metal oxide upholder or coating and coating order.In addition, mean CaO upholder using load potassium (K) as core as the metal oxide catalyst illustrative ' Cr/Mg/K-CaO catalyzer ' that carries with core-shell (core-shell) structure, successively coating magnesium (Mg) washing layer and chromium (Cr) washing layer and in forming the core-shell of coat (core-shell) structure carry metal oxide catalyst.
The preparation method of carrying the solid base catalyst of metal oxide is in the conventional supported catalyst preparation method who utilizes of catalyzer preparation field, can utilize for example precipitator method, load method, impregnation method etc.The solid base catalyst preparation method of representational year metal oxide comprises following continuous preparation process and carries out.For example comprise, the precursor compound that helps activated metal is dissolved in to distilled water and prepares the process that helps activated metal precursor solution; Add metal oxide and the process stirring of heating to the described activated metal precursor solution that helps; And load is helped to the metal oxide filtration drying of activated metal and gather in the crops the process of metal oxide of carrying.The described activated metal precursor compound that helps is also at the conventional compound utilizing of catalyzer preparation field, specifically can use the muriate of described metal, oxyhydroxide, sulfide, nitrate, carbonate, vitriol, acetate etc.In the present invention, more than a kind help activated metal precursor compound described can use in helping activated metal precursor solution preparation process.In addition, the described continuous activated metal loading process that helps can be implemented more than 2 times repeatedly.
In addition, in the present invention, by solid acid catalyst described above, solid base catalyst or these mixture use as catalyzer and make hydrocarbon compound prepare nitro paraffin compound at gas phase condition nitration reaction.
The hydrocarbon compound using in preparation in accordance with the present invention is the hydrocarbon compound of carbonatoms 1～40.Described hydrocarbon compound comprises whole straight chain types, and branching type is fully saturated, or the undersaturated hydrocarbon compound of part.Part unsaturated hydrocarbon compound refers to and comprises 1 above two key or the hydrocarbon compound of triple bond.Preferably use as hydrocarbon compound carbonatoms 1～4 gas phase hydrocarbon compound for example, methane gas, ethane gas, propane gas, butane gas, liquified petroleum gas (LPG) etc.
And, make the nitro agent of described hydrocarbon compound nitration reaction can use nitrous acid (NO 2), nitrogen tetroxide (N 2o 4), nitric acid (HNO 3) etc.
Nitrous acid (NO 2) in the situation of gas, by nitric acid and sulphur, with 5～15:0.5～6 volume ratio, the preferably volume ratio of 8～10:2～4 mixing, prepares and use in 150 ℃ of heating.In order to prevent that moisture content from entering nitrous acid (NO 2) the preparation feedback device inside of gas, can cooling pit be installed and remove moisture content.Nitrous acid (the NO of preparation 2) gas inflow reactor together with hydrocarbon compound is inner and make to carry out gas phase nitration reaction, because of the density variation of hydrocarbon and nitrous acid gas, by hydrocarbon in reactor and NO 2the effect that the even mixing of gas and can expecting improves the generation yield of nitro paraffin.
Nitration reaction under solid acid catalyst according to the present invention also can be implemented neatly under near condition normal pressure.Particularly, nitration reaction be by hydrocarbon compound with nitro agent to become 1:0.5～30 volume ratio, preferably 1:10～20 volume ratio is used, reaction pressure is near normal pressure, specifically maintain 0～1.5atm pressure range, temperature of reaction maintains 100～500 ℃, preferably the temperature range of 300～400 ℃ and implement nitration reaction 1～200 hour, preferred 1～100 hour.
, the preparation method of gas phase nitro paraffin in the past need maintain high pressure and hot conditions.But by the solid acid catalyst of motion of the present invention, solid base catalyst or these mixture use as catalyzer, also can prepare nitro paraffin by outstanding yield even if maintain temperature relatively low under condition of normal pressure.Thereby nitro paraffin preparation method of the present invention has not only can batch-type step, the advantage of can also continous way step carrying out.
[embodiment]
According to following preparation example and embodiment, as above the present invention of explanation is described in further detail, the invention is not restricted to this.
The preparation of ［ preparation example ］ catalyzer
[preparation example 1.H 11pMo 6v 6o 42the preparation of catalyzer]
Mix H 3pO 41.55g, MoO 36.48g and V 2o 5after 9.74g, be scattered in water 200ml, and after 95 ℃ of dissolvings, evaporation in the rotation thickner (rotary evaporator) that maintains 60 ℃, prepares H in 110 ℃ of the 2nd forced dryings after being dried 11pMo 6v 6o 42catalyzer.
[preparation example 2.H 11pMo 12o 40the preparation of catalyzer]
Mix H 3pO 4after 1.55g and MoO312.96g, be scattered in water 200ml, and after 95 ℃ of dissolvings, evaporation in the rotation thickner (rotary evaporator) that maintains 60 ℃, prepares H in 110 ℃ of the 2nd forced dryings after being dried 11pMo 12o 40catalyzer.
[preparation example 3.TiO 2-Al 2o 3the preparation of catalyzer]
By TiCl 424.89ml is dissolved in solution and the AlCl of frozen water 100ml 3the solution that 2.87g is dissolved in water 50ml mixes.Drip lentamente 28%NH as precipitation agent 3solution and be adjusted to pH8～9 and generate after coprecipitate, is utilized water washing 3 times, after the stove inner drying of 110 ℃, and sintering 3 hours the stoves of 480 ℃ (furnace) in and prepare TiO 2-Al 2o 3catalyzer.
[preparation example 4.TiO 2-ZrO 2the preparation of catalyzer]
By TiCl 424.89ml is dissolved in solution and the ZrOCl of frozen water 100ml 28H 2the solution that O4.95g is dissolved in water 50ml mixes.Drip lentamente 28%NH as precipitation agent 3solution and be adjusted to pH8～9 and generate after coprecipitate, is utilized water washing 3 times, after the stove inner drying of 110 ℃, and sintering 3 hours the stoves of 480 ℃ (furnace) in and prepare TiO 2-ZrO 2catalyzer.
[preparation example 5.TiO 2the preparation of-ZnO catalyst]
By TiCl 424.89ml is dissolved in solution and the ZnCl of frozen water 100ml 2the solution that 14.8g is dissolved in water 50ml mixes.Drip lentamente 28%NH as precipitation agent 3solution and be adjusted to pH8～9 and generate after coprecipitate, is utilized water washing 3 times, after the stove inner drying of 110 ℃, and sintering 3 hours the stoves of 480 ℃ (furnace) in and prepare TiO 2-ZnO catalyst.
[preparation example 6.TiO 2-MoO 3the preparation of catalyzer]
By TiCl 424.89ml is dissolved in solution and the (NH of frozen water 100ml 4) 2moO 4the solution that 12.3g is dissolved in water 50ml mixes.Drip lentamente 28%NH as precipitation agent 3solution and be adjusted to pH8～9 and generate after coprecipitate, is utilized water washing 3 times, after the stove inner drying of 110 ℃, and sintering 3 hours the stoves of 480 ℃ (furnace) in and prepare TiO 2-MoO 3catalyzer.
[preparation example 7.TiO 2-La 2o 3the preparation of catalyzer]
By TiCl 424.89ml is dissolved in solution and the La of frozen water 100ml 2o 3xH 2the solution that O5.84g is dissolved in water 50ml mixes.Drip lentamente 28%NH as precipitation agent 3solution and be adjusted to pH8～9 and generate after coprecipitate, is utilized water washing 3 times, after the stove inner drying of 110 ℃, and sintering 3 hours the stoves of 480 ℃ (furnace) in and prepare TiO 2-La 2o 3catalyzer.
[preparation example 8.TiO 2-WO 3the preparation of catalyzer]
By TiCl 424.89ml is dissolved in solution and the WO of frozen water 100ml 3the solution that 11.6g is dissolved in water 50ml mixes.Drip lentamente 28%NH as precipitation agent 3solution and be adjusted to pH8～9 and generate after coprecipitate, is utilized water washing 3 times, after the stove inner drying of 110 ℃, and sintering 3 hours the stoves of 480 ℃ (furnace) in and prepare TiO 2-WO 3catalyzer.
[preparation of 9～14. years fluorine O composite metallic oxide catalysts of preparation example]
By the metal oxide 10%CFCl separately of preparation in described preparation example 4～8 3solution-treated, and in 120 ℃ dry after, in air, prepare in 300 ℃ of sintering and carry a fluorine O composite metallic oxide catalyst.A year fluorine O composite metallic oxide catalyst for preparation is F-/TiO 2-Al 2o 3catalyzer (preparation example 9), F-/TiO 2-ZrO 2catalyzer (preparation example 10), F-/TiO 2-ZnO catalyst (preparation example 11), F-/TiO 2-MoO 3catalyzer (preparation example 12), F-/TiO 2-La 2o 3catalyzer (preparation example 13), F-/TiO 2-WO 3catalyzer (preparation example 14).
[preparation of preparation example 15.MgO catalyzer]
By Mg (NO 3) 26H 2o prepares MgO catalyzer in 600 ℃ of sintering 3 hours.
[preparation of preparation example 16.ZnO catalyzer]
By Zn (NO 3) 26H 2o33.84g is dissolved in H 2after O150ml, drip lentamente the ammonia solution (28～30%, SAMCHUN) as precipitation agent and be adjusted to pH8～9 and generate after throw out, utilize H 2o washing 3 times, and after the stove inner drying of 110 ℃, sintering 3 hours in the stove of 600 ℃ and making ZnO catalyzer.
[preparation of preparation example 17.CaO catalyzer]
By CaCl 215.37g be dissolved in H 2after O150ml, drip lentamente the ammonia solution (28～30%, SAMCHUN) as precipitation agent and be adjusted to pH8～9 and generate after throw out, utilize H 2o washing 3 times, and after the stove inner drying of 110 ℃, sintering 3 hours in the stove of 600 ℃ and preparation CaO catalyzer.
[preparation of preparation example 18.CaMgO catalyzer]
By Mg (NO 3) 26H 2o17.69g, CaCl 27.69g be dissolved in H 2after O150ml, drip lentamente the ammonia solution (28～30%, SAMCHUN) as precipitation agent and be adjusted to pH8～9 and generate after throw out, utilize H 2o washing 3 times, and after the stove inner drying of 110 ℃, sintering 3 hours in the stove of 600 ℃ and preparation CaMgO catalyzer.
[preparation of preparation example 19.CaZnO catalyzer]
By Zn (NO 3) 26H 2o16.92g, CaCl 27.69g be dissolved in H 2after O150ml, drip lentamente the ammonia solution (28～30%, SAMCHUN) as precipitation agent and be adjusted to pH8～9 and generate after throw out, utilize H 2o washing 3 times, and after the stove inner drying of 110 ℃, sintering 3 hours in the stove of 600 ℃ and preparation CaZnO catalyzer.
[preparation of preparation example 20.MgZnO catalyzer]
By Zn (NO 3) 26H 2o16.92g, Mg (NO 3) 26H 2o17.69g is dissolved in H 2after O150ml, drip lentamente the ammonia solution (28～30%, SAMCHUN) as precipitation agent and be adjusted to pH8～9 and generate after throw out, utilize H 2o washing 3 times, and after the stove inner drying of 110 ℃, sintering 3 hours in the stove of 600 ℃ and preparation MgZnO catalyzer.
[preparation of preparation example 21.Cr-CaO catalyzer]
As the precursor of Cr by Cr (NO 3) 39H 2o3.85g is dissolved in after distilled water 50ml, adds CaO upholder 4.5g to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and the Cr-CaO catalyzer of preparation load C r on CaO upholder.
[preparation of preparation example 22.Cr/K-CaO catalyzer]
Precursor as K is dissolved in KCl0.95g after distilled water 50ml, adds CaO upholder 4.5g to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and the K-CaO of preparation load K on CaO upholder.
Then, as the precursor of Cr by Cr (NO 3) 39H 2o3.85g is dissolved in after distilled water 50ml, adds the K-CaO4.5g of above-mentioned preparation to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and prepares using K-CaO as core (core), and outside surface forms the Cr/K-CaO catalyzer of the nucleocapsid structure of potassium (K) coat.
[preparation of preparation example 23.Cr/Mg-CaO catalyzer]
As the precursor of Mg by Mg (NO 3) 26H 2o5.27g is dissolved in after distilled water 50ml, adds CaO upholder 4.5g to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and the Mg-CaO of preparation load Mg on CaO upholder.
Then, as the precursor of Cr by Cr (NO 3) 39H 2o3.85g is dissolved in after distilled water 50ml, adds the Mg-CaO4.5g of above-mentioned preparation to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and prepares using Mg-CaO as core (core), and outside surface forms the Cr/Mg-CaO catalyzer of the nucleocapsid structure of chromium (Cr) coat.
[preparation of preparation example 24.K/Cr-CaO catalyzer]
As the precursor of Cr by Cr (NO 3) 39H 2o3.85g is dissolved in after distilled water 50ml, adds CaO upholder 4.5g to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and the Cr-CaO of preparation load C r on CaO upholder.
Then, as the precursor of K, KCl0.95g is dissolved in after distilled water 50ml, adds the Cr-CaO4.5g of above-mentioned preparation to this solution, and stir 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and prepares using Cr-CaO as core (core), and outside surface forms the K/Cr-CaO catalyzer of the nucleocapsid structure of potassium (K) coat.
[preparation of preparation example 25.K/Cr-CaMgO catalyzer]
As the precursor of Cr by Cr (NO 3) 39H 2o3.85g is dissolved in after distilled water 50ml, adds CaMgO upholder 4.5g to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and the Cr-CaMgO of preparation load C r on CaMgO upholder.
Then, as the precursor of K by KNO 31.61g is dissolved in after distilled water 50ml, adds the Cr-CaMgO4.5g of above-mentioned preparation to this solution, and stirs 3 hours in 70 ℃.Then, described reactant is utilized to H 2o washs the stove in 100 ℃ after 3 times and is dried and prepares using Cr-CaMgO as core (core), and outside surface forms the K/Cr-CaMgO catalyzer of the nucleocapsid structure of potassium (K) coat.
The preparation of ［ embodiment ］ nitro paraffin
[embodiment 1～14. utilizes nitropropane synthetic of solid acid catalyst]
For making nitrous acid (NO 2) gas generation, put into nitric acid 1kg and sulphur 40g, utilize bar magnet to stir, and with 150 ℃ of temperature heating.Fill the solid acid catalyst 0.2g separately of preparation in described preparation example 1～14 to other reactor, by the nitrous acid (NO generating 2) gas puts into reactor together with propane gas.In order to understand with the yield of the nitro paraffin of temperature of reaction, temperature of reaction is implemented to experiment from 250 variations to 400 ℃.Resultant of reaction uses gas chromatographic analysis.The results are shown in following table 1.
［ table 1 ］
Figure BDA0000472300780000141
Figure BDA0000472300780000151
According to described embodiment 1～14, in the time using the nitration reaction of implementing propane under the condition of solid acid catalyst of the present invention, confirm the tendency that the transformation efficiency of the transformation efficiency of propane propane along with temperature rise rises gradually.Confirm that the yield of nitropropane is at 325～375 ℃ of the highest yields of demonstration of temperature of reaction, more than temperature of reaction is brought up to described temperature range, instead the yield of nitropropane reduces.Substantially, reaction and the catalyst-free condition under the solid acid catalyst of embodiment 1～14 exists relatively obtains the effect that yield improves significantly.In addition, carrying a fluorine O composite metallic oxide catalyst is load fluorine anion (F-) again on metal oxide, through confirming that yield raises in the time preparing nitro paraffin.
[embodiment 15～25. utilizes nitropropane synthetic of solid base catalyst]
For making nitrous acid gas (NO 2) generate, put into nitric acid 1kg and sulphur 40g, utilize bar magnet to stir, and with 150 ℃ of temperature heating.Fill to other reactor after the solid base catalyst 0.2g separately of preparation in described preparation example 15～25, by the nitrous acid gas (NO of propane gas and above-mentioned generation 2) put into together reactor.For understanding is implemented experiment by temperature of reaction from 250 ℃ of variations to 400 ℃ with the yield of the nitro paraffin of temperature of reaction.Use gas chromatography for analyze the resultant of reaction obtaining under each temperature of reaction condition, the results are shown in following table 2.
［ table 2 ］
Figure BDA0000472300780000171
According to the result of described table 2, implement the nitration reaction of propane under the condition that uses solid base catalyst of the present invention time, the tendency that the transformation efficiency of confirmation propane along with temperature rise rises gradually.Substantially, reaction and the comparison of catalyst-free condition under the solid base catalyst of embodiment 15～25 exists, obtain the effect that yield improves significantly.
Be selected from CaO in use, in the reaction (embodiment 15～17) of the solid base catalyst of the metal oxide of MgO and ZnO, confirm, in the time of 325～375 ℃ of temperature of reaction, the yield of nitropropane is the highest, and more than temperature of reaction is brought up to described temperature range, instead the yield of nitropropane reduces.In addition, using as CaMgO, CaZnO, in the reaction (embodiment 17～20) of the solid base catalyst of the complex metal oxides of MgZnO, in the time of 250～300 ℃ of temperature of reaction, the not only transformation efficiency of propane, the yield of nitro-compound is also the highest.That is, compare the solid base catalyst of single metal oxide, use the solid base catalyst of complex metal oxides can expect to reduce the effect of temperature of reaction.
In addition, using to the upholder load of CaO metal oxide as K, Mg, in the reaction (embodiment 21～25) of the solid base catalyst that carries metal oxide that helps activated metal of Cr, in the time of 300 ℃, the yield of nitropropane is the highest.With the nitration reaction comparison under CaO metal oxide catalyst (embodiment 17), the yield that obtains the highest 400% left and right at identical temperature condition increases effect, even temperature of reaction is reduced to 250 ℃ of left and right, also can obtain nitro paraffin with the yield of embodiment 17 equities.In addition, in the reaction (embodiment 25) of the K/Cr-CaMgO catalyzer using the complex metal oxides of CaMgO as upholder in use, compare the K/Cr-CaO catalyzer (embodiment 24) using the single metal oxide of CaO as upholder, the not only transformation efficiency of propane, also obtain nitro-compound yield improve effect.Thereby the upholder that combines aptly metal oxide forms solid base catalyst of the present invention with helping activated metal, use and can expect outstanding activity as nitro paraffin catalyst for preparing.
[industrial applicibility]
As above observe, even if the nitro paraffin preparation method under the solid acid catalyst of motion of the present invention or solid base catalyst existence implements gas phase nitration reaction in condition of normal pressure, yield that also can be fully high obtains nitro paraffin.Especially, nitro paraffin preparation method of the present invention not only can batch-type step, can also continous way step be carried out by reaction, so high as payable production method utility value.
Claims (according to the modification of the 19th article of treaty)
1. the preparation method of nitro paraffin, is characterized in that, making the hydrocarbon compound of carbonatoms 1～40 and the nitro agent of gas phase react and prepare in the method for nitro paraffin, using nitrous acid gas as described nitro agent, uses as nitration reaction catalyzer:
(a) be selected from following a kind of above solid acid catalyst: under show the heteropolyacid shown in Chemical formula 1; Be selected from TiO 2-Al 2o 3, TiO 2-ZrO 2, TiO 2-ZnO, TiO 2-MoO 3, TiO 2-La 2o 3and TiO 2-WO 3complex metal oxides on load fluorine anion (F-) carry fluorine complex metal oxides, or
(b) be selected from a kind of following above solid base catalyst: make its load be selected from K as upholder the metal oxide that comprises the a kind of above metal being selected from Ca, Mg and Zn, 1 kind of above metal oxide that carries that helps activated metal in Mg and Cr, or
(c) described solid acid catalyst (a) and the mixture of solid base catalyst (b), and
Make carry out gas phase nitration reaction and prepare under the temperature condition of the pressure of 0～1.5atm and 100～500 ℃:
[Chemical formula 1]
H 11PM 12-xO 42-y
In described Chemical formula 1, M is Mo 5+, V 2+, or its hybrid metal, x and y meet 0≤x≤12, the real number of 0≤y≤12.
2. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid acid catalyst of described heteropolyacid is selected from H 3pMo 12o 40and H 11pMo 6v 6o 42.
3. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid acid catalyst of described year fluorine complex metal oxides is selected from F-/TiO 2-Al 2o 3, and F-/TiO 2-ZrO 2.
4. the preparation method of the nitro paraffin of claim 1, is characterized in that, the metal oxide containing in described solid base catalyst is selected from CaO, MgO, ZnO, CaMgO, CaZnO, MgZnO, and CaMgZnO.
5. the preparation method of the nitro paraffin of claim 1, is characterized in that, the metal oxide that carries containing in described 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.
6. the preparation method of the nitro paraffin of any one of claim 1～5, is characterized in that, nitration reaction is implemented with continous way step or batch-type step.
7. the preparation method of the nitro paraffin of any one of claim 1～5, is characterized in that, appropriate hydrocarbon gas and nitro agent are used with 1:5～30 volume ratio scope.

Claims (10)

1. the preparation method of nitro paraffin, is characterized in that making the hydrocarbon compound of carbonatoms 1～40 and the nitro agent of gas phase react and prepare in the method for nitro paraffin, uses as described nitration reaction catalyzer:
(a) be selected from following a kind of above solid acid catalyst: under show the heteropolyacid shown in Chemical formula 1; Be selected from TiO 2-Al 2o 3, TiO 2-ZrO 2, TiO 2-ZnO, TiO 2-MoO 3, TiO 2-La 2o 3and TiO 2-WO 3complex metal oxides; And on described complex metal oxides load fluorine anion (F-) carry fluorine complex metal oxides; Or
(b) be selected from a kind of following above solid base catalyst: the metal oxide that comprises the a kind of above metal being selected from Ca, Mg and Zn; And make its load be selected from K as upholder the metal oxide that comprises the a kind of above metal being selected from Ca, Mg and Zn, a kind of above metal oxide that carries that helps activated metal in Mg and Cr; Or
(c) described solid acid catalyst (a) and the mixture of solid base catalyst (b):
[Chemical formula 1]
H 11PM 12-xO 42-y
In described Chemical formula 1, M is Mo 5+, V 2+, or its hybrid metal, x and y meet 0≤x≤12, the real number of 0≤y≤12.
2. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid acid catalyst of described heteropolyacid is selected from H 3pMo 12o 40, and H 11pMo 6v 6o 42.
3. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid acid catalyst of described complex metal oxides is selected from TiO 2-Al 2o 3, and TiO 2-ZrO 2.
4. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid acid catalyst of described year fluorine complex metal oxides is selected from F-/TiO 2-Al 2o 3, and F-/TiO 2-ZrO 2.
5. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid base catalyst of described metal oxide is selected from CaO, MgO, ZnO, CaMgO, CaZnO, MgZnO, and CaMgZnO.
6. the preparation method of the nitro paraffin of claim 1, is characterized in that, the solid base catalyst of described year metal oxide 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.
7. the preparation method of the nitro paraffin of any one of claim 1～6, is characterized in that, nitration reaction is implemented under the temperature condition of the pressure of 0～1.5atm and 100～500 ℃.
8. the preparation method of the nitro paraffin of any one of claim 1～6, is characterized in that, nitration reaction is implemented with continous way step or batch-type step.
9. the preparation method of the nitro paraffin of any one of claim 1～6, is characterized in that, appropriate hydrocarbon gas and nitro agent are used with 1:5～30 volume ratio scope.
10. the preparation method of the nitro paraffin of claim 9, is characterized in that, described nitro agent is selected from nitrous acid gas (NO 2), nitrogen tetroxide gas (N 2o 4) and nitric acid gas (HNO 3).
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EP0134265A1 (en) * 1982-02-25 1985-03-20 The Dow Chemical Company Catalytic preparation of nitroalkanes from alkanes
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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
KR20110070080A (en) * 2009-12-18 2011-06-24 한국화학연구원 Preparing method of nitroparaffin using solid acidic catalyst

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