CN102219694A - Method for preparing C1-C4 alkyl nitrite ester - Google Patents
Method for preparing C1-C4 alkyl nitrite ester Download PDFInfo
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- CN102219694A CN102219694A CN2010101469884A CN201010146988A CN102219694A CN 102219694 A CN102219694 A CN 102219694A CN 2010101469884 A CN2010101469884 A CN 2010101469884A CN 201010146988 A CN201010146988 A CN 201010146988A CN 102219694 A CN102219694 A CN 102219694A
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Abstract
The invention relates to a method for preparing C1-C4 alkyl nitrite ester. The use of the method is aimed to mainly solving the technical problem of low selectivity of the target product alkyl nitrite ester in the prior art. In the method, a technical scheme is adopted as follows: the method comprises the following steps: (a) leading raw materials: nitric oxide, C1-C4 alkanol and first oxygen into a super-gravity field reactor of a first revolving bed for reaction, thus obtaining gas-phase reaction effluent I containing the alkyl nitrite ester, gas-phase reaction effluent I containing unreacted nitric oxide and liquid-phase reaction effluent I containing unreacted C1-C4 alkanol; and (b) leading the gas-phase reaction effluent I, the liquid-phase reaction effluent I and at least second oxygen into at least a super-gravity field reactor of a second revolving bed, so as to obtain the alkyl nitrite ester after the reaction effluent is subjected to separation, thus better solving the problem of the low selectivity of the target product-the alkyl nitrite ester and being used for industrial production of increasing the C1-C4 alkyl nitrite ester.
Description
Technical field
The present invention relates to a kind of C
1～C
4The preparation method of alkyl nitrous acid ester is particularly about the required C of CO coupling producing oxalic ester
1～C
4The preparation method of alkyl nitrous acid ester.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.Enter 21 century, barkite is subjected to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare crucial industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, production technique cost height, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking an operational path that cost is low, environment is good always.The sixties in last century, the D.F.Fenton of U.S. Associated Oil Company finds, carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative coupling method synthesis of oxalate and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer easily runs off in the reaction process.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
The reaction process of synthesis of oxalate is as follows:
Linked reaction 2CO+2RONO → 2NO+ (COOR)
2(1)
Regenerative response 2ROH+0.5O
2+ 2NO → 2RONO+H
2O (2)
By said process as can be known the key problem in technology of this system be to make the high efficiency reasonable use of NO, RONO, ROH highly selective in the two-step reaction process.
But practical situation are in the reaction process of step (2), except generating principal product alkyl nitrous acid ester; also often have side reaction and take place, especially have the rare nitric acid of by product to generate, this must consume more NO gases; increase energy consumption and cost, also can bring equipment corrosion etc. simultaneously.Although more about document how to produce the alkyl nitrous acid ester, the relevant selectivity that how effectively to improve alkyl nitrite prevents that better the report of nitric acid side reaction generation is less.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopt vapor phase process, CO is under the participation of ethyl nitrite, under the catalysis of bimetal loaded catalyst, coupling generates the oxalic acid diethyl ester crude product, reaction is self-enclosed working cycle, CO gas enters coupler reactor with ethyl nitrite from regeneration reactor through mixing preheating, reaction back gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, the non-condensable gas that contains NO enters regeneration reactor, in regeneration reactor and ethanol, the recirculation of oxygen reaction generation ethyl nitrite is returned coupler reactor and is used continuously, does not mention the selectivity of ethyl nitrite among the present invention.
Document CN 95116136.9 discloses the catalyzer of the synthetic usefulness of a kind of barkite, selects for use Zr to make auxiliary agent, develops novel Pd-Zr/Al with pickling process
2O
3Catalyzer.This catalyzer is to adopt fixed-bed reactor as carbon monoxide and the reaction of nitrous acid ester synthesis of oxalic ester by gaseous catalysis.Equally, this patent does not relate to the selectivity of nitrous acid ester and drawing up of side reaction nitric acid yet.
The EP0023745A3 patent that Britain Imperial Chemical Industries (ICI) propose is mentioned rotating bed and be can be used for processes such as absorption, parsing, distillation, but does not disclose the utilisation technology of industrially scalable.CN1064338A discloses the method for utilizing rotating bed to carry out the oil-field flooding deoxidation; CN1116146A discloses a kind of method for preparing ultrafine particle under super gravity field.
The super gravity field technology is the new technology that early eighties just occurs, and its internal mechanism is also continuing exploration, and research for application and development is still constantly being carried out, and new Application Areas also is applied to C about rotating bed for now also in continuous developing
1～C
4The report that the alkyl nitrous acid ester is produced.
Summary of the invention
Technical problem to be solved by this invention is the C that in the past exists in the document
1～C
4The technical problem that alkyl nitrous acid ester selectivity is low provides a kind of new C
1～C
4The preparation method of alkyl nitrous acid ester.This method has C
1～C
4The advantage that alkyl nitrous acid ester selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of C
1～C
4The preparation method of alkyl nitrous acid ester comprises the steps:
A) raw material oxynitride, C
1～C
4Alkanol and first strand of oxygen enter the first rotating bed super gravity field reactor and react, and obtain containing the gas-phase reaction effluent I of alkyl nitrite and unreacted nitrogen oxide compound and contain unreacted C
1～C
4The liquid phase reaction effluent I of alkanol;
B) gas-phase reaction effluent I, liquid phase reaction effluent I and at least the second strand of oxygen enter at least the second rotating bed super gravity field reactor and react, and obtain containing the reaction effluent II and the liquid phase reaction effluent III of alkyl nitrous acid ester;
C) after separating, obtain the alkyl nitrous acid ester from the reaction effluent II that contains the alkyl nitrous acid ester in the step b) with liquid phase reaction effluent III;
Wherein, all be fixed with the protruded packing layer on the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor, raw material in the rotating bed super gravity field reactor with adverse current, and stream or the mode of cross-flow by the protruded packing layer.
Oxynitride is selected from NO, N in the technique scheme
2O
3Or NO
2In one or more mixed gas, contain NO in the described oxynitride, the big NO of NO mole number
2Mole number; First strand of oxygen is 0.1～10: 1 with the ratio of the mole number of second strand of oxygen, and the preferred molar ratio scope is 0.2～8: 1, and more preferably molar ratio range is 0.2～5: 1.
The reaction conditions of the first rotating bed super gravity field reactor is in the technique scheme: temperature of reaction is 0～100 ℃, and reaction pressure is-0.09～1.5MPa, C
1～C
4Alkanol is 1～100: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～50: 1 with the ratio of the mole number of total oxygen; The preferred reaction conditions of the first rotating bed super gravity field reactor is: temperature of reaction is 10～80 ℃, and reaction pressure is-0.05～1.0MPa, C
1～C
4Alkanol is 1～50: 1 with the ratio of the mole number of oxynitride, and oxynitride is 5～20: 1 with the ratio of the mole number of total oxygen; The reaction conditions of the second rotating bed super gravity field reactor is: temperature of reaction is 0～100 ℃, and reaction pressure is-0.09～1.5MPa; The preferred reaction conditions of the second rotating bed super gravity field reactor is: temperature of reaction is 10～80 ℃, and reaction pressure is-0.05～1.0MPa.
The rotating speed of the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor is 100～5000rpm in the technique scheme, and preferred speed range is 300～4000rpm.C
1～C
4Alkanol is preferably from methyl alcohol, ethanol or n-propyl alcohol, and more preferably scheme is selected from methyl alcohol or ethanol.
As everyone knows, all substances are all attracted by the earth because of gravity on the earth, super gravity field is the environment more much bigger than earth gravity intensity of field, and material suffered power under super gravity field is called hypergravity, utilizes hypergravity the principles of science and the practical technique that produces is called high-gravity technology.
High-gravity technology is a new technology of strengthening polyphasic flow transmission and reaction process, since eighties of last century is come out, at home and abroad be subjected to paying attention to widely, because its broad applicability and have that the volume that legacy equipment do not have is little, in light weight, energy consumption is low, easy running, easy-maintaining, safety, advantage such as can conform reliably, flexibly and more, make high-gravity technology in industrial circles such as environmental protection and material biochemical industry, wide commercial applications prospect be arranged.But high-gravity technology also mainly is in the application and development stage at present, embodies a concentrated reflection of the gas-solid fluidization technology of hypergravity and two aspects of hypergravity gas-liquid mass transferring technology.
Under the hypergravity environment bigger hundreds of times to thousand times than earth gravity field, great shear forces is torn into liquid liquid film, brin, the drop of micron to nano grade, produce phase interface huge, fast updating, greatly increased the gas-to-liquid contact specific surface area, make 1～3 order of magnitude of raising in the interphase mass transfer speed ratio tradition tower, microcosmic mixes and mass transfer process is greatly strengthened.Make the production efficiency of unit equipment volume obtain the raising of 1～2 order of magnitude.
The rotating bed super gravity field device, as the equipment that produces super gravity field, it is made up of gas and liquid inlet tube, rotor, gas and liquid exit usually.Its principle of work be gas phase through gas inlet tube by tangential introducing rotor exocoel, under the effect of gaseous tension, enter filler by rotor outer rim place.Liquid is introduced rotor internal cavity by liquid inlet tube, through the shower nozzle sprinkle on the rotor inner edge.The liquid that enters rotor is subjected to the effect of filler in the rotor, and circumferential speed increases, and the centrifugal force that is produced pushes it against the rotor outer rim.In this process, liquid is by fillers dispersed, the broken surface-area that forms greatly, brings in constant renewal in, and the zigzag runner has aggravated the renewal of fluid surface.Like this, fabulous mass transfer and reaction conditions have been formed at internal rotor.Liquid is thrown by rotor that shell compiles after liquid outlet tube leaves overweight machine.Gas leaves rotor from rotor center, is drawn by gas outlet tube, finishes mass transfer and reaction process.
Studies show that, in the process of oxynitride and oxygen and alcohol generation oxidative esterification reaction generation alkyl nitrite, reaction conditions, comprise temperature of reaction, reaction pressure, the hybrid mode of the residence time and oxynitride, oxygen and alcohol and proportioning etc. all produce oxynitride generation N in remarkably influenced, the especially generation of nitric acid side reaction and the raw material to the selectivity of nitrous acid ester
2O
4Reaction substantial connection is arranged, prevent N
2O
4Generation be key problem in technology.The present inventor finds that in research process the selectivity of the injection mode of oxygen and alkyl nitrous acid ester has substantial connection, and the concentration of partial oxygen is high more, N
2O
4It is just big more to generate probability, and the dispersiveness of oxygen is good more, and the concentration of partial oxygen is low more, N
2O
4It is just low more to generate probability, and the selectivity of nitrous acid ester is just high more.Studying the reaction of also finding oxynitride and oxygen and alcohol generation oxidative esterification generation alkyl nitrite is fast response, and the reaction of side reaction generation nitric acid etc. is slow slightly; The speed of reaction of NO oxidative esterification reaction process mainly is subjected to the influence of gas-liquid resistance to mass transfer, if effectively improve gas-liquid mass transfer efficient, can effectively reduce N
2O
4The generation probability, and then prevent the generation of side reactions such as nitric acid; Technical solution of the present invention is on the basis of the characteristics of fully studying oxynitride and oxygen and alcohol generation oxidative esterification reaction, adopting the oxygen segmentation to inject and adopt the rotating bed super gravity field reactor is reacting environment, make full use of the significant advantage that can how much orders of magnitude significantly improves gas-liquid mass transfer speed of rotating bed super gravity field device, and the advantage that oxygen can effectively reduce partial oxygen concentration is annotated in segmentation, and then effectively promote main reaction, the draw up generation of side reaction, improve utilization ratio of raw materials such as NO, greatly improved the selectivity of alkyl nitrous acid ester.
Adopting technical scheme of the present invention, is 10～80 ℃ in the temperature of reaction of the first rotating bed super gravity field reactor, and reaction pressure is-0.05～1.0MPa, C
1～C
4Alkanol is 1～50: 1 with the ratio of the mole number of oxynitride, and oxynitride is 5～20: 1 with the ratio of the mole number of first strand of oxygen; The temperature of reaction of the second rotating bed super gravity field reactor is 10～80 ℃, and reaction pressure is-0.05～1.0MPa, and first strand of oxygen is 0.2～5: 1 with the ratio of the mole number of at least the second strand of oxygen; The rotating speed of the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor is under 300～4000rpm condition, and its reaction result is: the selectivity of alkyl nitrous acid ester can obtain better technical effect greater than 99%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1～11]
Oxynitride is selected from NO, raw material NO, C
1～C
4Alkanol and first strand of oxygen enter the first rotating bed super gravity field reactor and react, the liquid phase reaction effluent I that obtains containing the gas-phase reaction effluent I of alkyl nitrous acid ester and unreacted nitrogen oxide compound and contain unreacted alkanol; Gas-phase reaction effluent I, liquid phase reaction effluent I and second strand of oxygen enter the second rotating bed super gravity field reactor and react, obtain containing the reaction effluent II and the liquid phase reaction effluent III of alkyl nitrous acid ester, after separating, obtain the alkyl nitrous acid ester.Wherein, all be fixed with the protruded packing layer on the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor, and the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor be all with rotating bed super gravity field reactor among the embodiment 1 among the patent CN1895766A identical (as follows), raw material in the rotating bed super gravity field reactor with and the mode of stream by the protruded packing layer.The rotating speed of the rotor of the first and second rotating bed super gravity field devices is 1500rpm, and the result under its differential responses condition is as shown in table 1:
The selectivity of the alkyl nitrous acid ester under the table 1 differential responses condition
[embodiment 12]
Oxynitride is selected from NO and NO
2Mol ratio be 3: 1 mixture, raw material oxynitride, methyl alcohol and first strand of oxygen enter the first rotating bed super gravity field reactor and react, the liquid phase reaction effluent I that obtains containing the gas-phase reaction effluent I of alkyl nitrite and unreacted nitrogen oxide compound and contain unreacted methanol; Gas-phase reaction effluent I, liquid phase reaction effluent I and second strand of oxygen enter the second rotating bed super gravity field reactor and react, and obtain containing the reaction effluent II and the liquid phase reaction effluent III of methyl nitrite, obtain methyl nitrite after separating.Wherein, all be fixed with the protruded packing layer on the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor, raw material mode with adverse current in the rotating bed super gravity field reactor is passed through the protruded packing layer.Reaction conditions at the first rotating bed super gravity field reactor is: temperature of reaction is 20 ℃, and reaction pressure is-0.05MPa, and methyl alcohol is 2: 1 with the ratio of the mole number of NO, and NO is 6: 1 with the ratio of the mole number of total oxygen; The reaction conditions of the second rotating bed super gravity field reactor is: temperature of reaction is 30 ℃, and reaction pressure is 0.05MPa; First strand of oxygen is 0.5: 1 with the ratio of the mole number of second strand of oxygen, the rotating speed of the rotor of the first rotating bed super gravity field reactor is 1000rpm, the rotating speed of the rotor of the second rotating bed super gravity field reactor is under the 2000rpm condition, and its result is: the selectivity of methyl nitrite is 99.58%.
[embodiment 13]
Oxynitride is selected from NO, raw material NO, methyl alcohol and first strand of oxygen enter the first rotating bed super gravity field reactor and react, the liquid phase reaction effluent I that obtains containing the gas-phase reaction effluent I of methyl nitrite and unreacted nitrogen oxide compound and contain unreacted methanol; Gas-phase reaction effluent I, liquid phase reaction effluent I and second strand of oxygen enter the second rotating bed super gravity field reactor and react, and obtain containing the reaction effluent II and the liquid phase reaction effluent III of methyl nitrite, obtain methyl nitrite after separating.Wherein, all be fixed with the protruded packing layer on the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor, raw material passes through the protruded packing layer in the mode that also flows in the rotating bed super gravity field reactor.Reaction conditions at the first rotating bed super gravity field reactor is: temperature of reaction is 30 ℃, and reaction pressure is-0.02MPa, and methyl alcohol is 3: 1 with the ratio of the mole number of NO, and NO is 5: 1 with the ratio of the mole number of total oxygen; The reaction conditions of the second rotating bed super gravity field reactor is: temperature of reaction is 40 ℃, and reaction pressure is 0.06MPa; First strand of oxygen is 1: 1 with the ratio of the mole number of second strand of oxygen, the rotating speed of the rotor of the first rotating bed super gravity field reactor is 1500rpm, the rotating speed of the rotor of the second rotating bed super gravity field reactor is under the 2500rpm condition, and its result is: the selectivity of methyl nitrite is 99.48%.
[embodiment 14]
Oxynitride is selected from NO, raw material NO, methyl alcohol and first strand of oxygen enter the first rotating bed super gravity field reactor and react, the liquid phase reaction effluent I that obtains containing the gas-phase reaction effluent I of methyl nitrite and unreacted nitrogen oxide compound and contain unreacted methanol; Gas-phase reaction effluent I, liquid phase reaction effluent I and second strand of oxygen enter the second rotating bed super gravity field reactor and react, and obtain containing the reaction effluent II and the liquid phase reaction effluent III of methyl nitrite; Reaction effluent II, liquid phase reaction effluent III and the 3rd strand of oxygen enter the 3rd rotating bed super gravity field reactor and react, and obtain containing the reaction effluent III and the liquid phase reaction effluent IV of methyl nitrite, obtain methyl nitrite after separating.Wherein, all be fixed with the protruded packing layer on the rotor of the first rotating bed super gravity field reactor, the second rotating bed super gravity field reactor and the 3rd rotating bed super gravity field reactor, raw material all passes through the protruded packing layer in the mode that also flows in the rotating bed super gravity field reactor.Reaction conditions at the first rotating bed super gravity field reactor is: temperature of reaction is 30 ℃, and reaction pressure is-0.02MPa, and methyl alcohol is 3: 1 with the ratio of the mole number of NO, and NO is 5: 1 with the ratio of the mole number of total oxygen; The reaction conditions of the second rotating bed super gravity field reactor and the 3rd rotating bed super gravity field reactor is: temperature of reaction is 30 ℃, and reaction pressure is 0.02MPa; First strand of oxygen and second strand of oxygen are 1: 1: 1 with the ratio of the mole number of the 3rd strand of oxygen, the rotating speed of the rotor of the first rotating bed super gravity field reactor is 1500rpm, the rotating speed of the rotor of the second rotating bed super gravity field reactor and the 3rd rotating bed super gravity field reactor is under the 2000rpm condition, and its result is: the selectivity of methyl nitrite is 99.88%.
[comparative example 1]
According to embodiment 8 identical condition and reaction raw materials, just two reactors all adopt fixed-bed reactor, and its result is: the selectivity of methyl nitrite is 92.5%.
[comparative example 2]
According to embodiment 8 identical condition and reaction raw materials, just not segmentation of oxygen is injected, and its result is: the selectivity of methyl nitrite is 98.9%.
Claims (8)
1. C
1～C
4The preparation method of alkyl nitrous acid ester comprises the steps:
A) raw material oxynitride, C
1～C
4Alkanol and first strand of oxygen enter the first rotating bed super gravity field reactor and react, and obtain containing the gas-phase reaction effluent I of alkyl nitrite and unreacted nitrogen oxide compound and contain unreacted C
1～C
4The liquid phase reaction effluent I of alkanol;
B) gas-phase reaction effluent I, liquid phase reaction effluent I and at least the second strand of oxygen enter at least the second rotating bed super gravity field reactor and react, and obtain containing the reaction effluent II and the liquid phase reaction effluent III of alkyl nitrous acid ester;
C) after separating, obtain the alkyl nitrous acid ester from the reaction effluent II that contains the alkyl nitrous acid ester in the step b) with liquid phase reaction effluent III;
Wherein, all be fixed with the protruded packing layer on the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor, raw material in the rotating bed super gravity field reactor with adverse current, and stream or the mode of cross-flow by the protruded packing layer.
2. according to the described C of claim 1
1～C
4The preparation method of alkyl nitrous acid ester is characterized in that oxynitride is selected from NO, N
2O
3Or NO
2In one or more mixed gas, contain NO in the described oxynitride, the NO mole number is greater than NO
2Mole number; First strand of oxygen is 0.1～10: 1 with the ratio of the mole number of at least the second strand of oxygen.
3. according to the described C of claim 1
1～C
4The preparation method of alkyl nitrous acid ester, the temperature of reaction that it is characterized in that the first rotating bed super gravity field reactor is 0～100 ℃, reaction pressure is-0.09～1.5MPa, C
1～C
4Alkanol is 1～100: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～50: 1 with the ratio of the mole number of total oxygen; The temperature of reaction of the second rotating bed super gravity field reactor is 0～100 ℃, and reaction pressure is-0.09～1.5MPa, and first strand of oxygen is 0.2～8: 1 with the ratio of the mole number of at least the second strand of oxygen.
4. according to the described C of claim 3
1～C
4The preparation method of alkyl nitrous acid ester, the temperature of reaction that it is characterized in that the first rotating bed super gravity field reactor is 10～80 ℃, reaction pressure is-0.05～1.0MPa, C
1～C
4Alkanol is 1～50: 1 with the ratio of the mole number of oxynitride, and oxynitride is 5～20: 1 with the ratio of the mole number of total oxygen; The temperature of reaction of the second rotating bed super gravity field reactor is 10～80 ℃, and reaction pressure is-0.05～1.0MPa, and first strand of oxygen is 0.2～5: 1 with the ratio of the mole number of at least the second strand of oxygen.
5. according to the described C of claim 1
1～C
4The preparation method of alkyl nitrous acid ester is characterized in that the rotating speed of the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor is 100～5000rpm.
6. according to the described C of claim 5
1～C
4The preparation method of alkyl nitrous acid ester is characterized in that the rotating speed of the rotor of the first rotating bed super gravity field reactor and the second rotating bed super gravity field reactor is 300～4000rpm.
7. according to the described C of claim 1
1～C
4The preparation method of alkyl nitrous acid ester is characterized in that: C
1～C
4Alkanol is selected from methyl alcohol, ethanol or n-propyl alcohol.
8. according to the described C of claim 7
1～C
4The preparation method of alkyl nitrous acid ester is characterized in that: C
1～C
4Alkanol is selected from methyl alcohol or ethanol.
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|---|---|---|---|
| CN201010146988.4A CN102219694B (en) | 2010-04-15 | 2010-04-15 | Method for preparing C1-C4 alkyl nitrite ester |
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| CN102219694B (en) | 2014-01-22 |
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