CN101993374A - Method for preparing C1-C4 alkyl nitrites - Google Patents
Method for preparing C1-C4 alkyl nitrites Download PDFInfo
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- CN101993374A CN101993374A CN2009100578453A CN200910057845A CN101993374A CN 101993374 A CN101993374 A CN 101993374A CN 2009100578453 A CN2009100578453 A CN 2009100578453A CN 200910057845 A CN200910057845 A CN 200910057845A CN 101993374 A CN101993374 A CN 101993374A
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Abstract
The invention relates to a method for preparing C1-C4 alkyl nitrites, which mainly solves the technical problems of low target product selectivity and high content of nitric acid as side products in the prior art. The method comprises the following steps of: a, enabling nitric oxide and oxygen to firstly enter a reactor I, reacting to generate an effluent I containing NO2 and unreacted NO; b, enabling the effluent I and C1-C4 alkanols to enter a reactor II, reacting to generate an effluent II containing the nitrites; and c, obtaining the nitrites after separating the effluent II containing the nitrites, enabling the nitrites subjected to the dryness to enter a subsequent reaction unit for use, wherein the nitric oxide contains the NO, and the mol number of the NO is more than that of the NO2, the mol ratio of the NO to the oxygen in the nitric oxide is 4-25:1. The invention better solves the problems, and can be used in the industrialized production for increasing the yield of C1-C4 alkyl nitrites.
Description
Technical field
The present invention relates to a kind of preparation C
1～C
4The method of alkyl nitrous acid ester is particularly about the required C of CO coupling producing oxalic ester
1～C
4The production 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 0.5MP, 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+0.502+2NO → 2RONO+H20 (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.
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, the side reaction product nitric acid content is high provides a kind of new preparation C
1～C
4The method of alkyl nitrous acid ester.This method has C
1～C
4Alkyl nitrous acid ester selectivity height, the advantage that the side reaction product nitric acid content is low.
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 preparation C
1～C
4The method of alkyl nitrous acid ester comprises the steps:
A) oxynitride and oxygen at first enter reactor I, contact with aluminosilicate catalyst, and reaction generates and contains NO
2And the effluent I of unreacted NO;
B) effluent I and C
1～C
4Alkanol enters reactor II, and reaction generates and contains C
1～C
4The effluent II of alkyl nitrous acid ester;
C) contain C
1～C
4The effluent II of alkyl nitrous acid ester obtains C after separating
1～C
4The alkyl nitrous acid ester uses by entering the subsequent reactions unit after the drying treatment again;
Wherein, oxynitride is selected from NO, N
2O
3Or NO
2In one or more mixed gas, contain NO in the described oxynitride, the big NO of NO mole number
2Mole number; In the step a) in the oxynitride ratio of NO and the mole number of oxygen be 4～25: 1.
In the technique scheme, the aluminosilicate catalyst preferred version is selected from least a among ZSM-5, β-molecular sieve, y-zeolite or the MCM-22, and more preferably scheme is selected from ZSM-5; The Si/Al mol ratio of aluminosilicate catalyst is 10～800: 1, and preferable range is 20～500: 1.
The reaction conditions of reactor I is in the technique scheme: temperature of reaction is 40～180 ℃, and reaction pressure is-0.05～1.0MPa, and reaction contact time is 0.05～100 second, and the NO in the oxynitride is 4～20: 1 with the ratio preferable range of the mole number of oxygen.The preferred reaction conditions of reactor I is: the temperature of reaction preferable range is 80～170 ℃, more preferably scope is 121～170 ℃, best preferable range is 125～160 ℃, reaction pressure is 0.01～0.8MPa, reaction contact time is 2～50 seconds, in the oxynitride ratio of NO and the mole number of oxygen more preferably scope be 4～15: 1.The better preferable reaction temperature of reactor I is 150～158 ℃.
The reaction conditions of reactor II is in the technique scheme: temperature of reaction is 20～100 ℃, and reaction pressure is-0.05～1.0MPa, and reaction contact time is 0.05～200 second, C
1～C
4The ratio of the mole number of NO is 2～15: 1 among alkanol and the effluent I.The preferred reaction conditions of reactor II is: temperature of reaction is 30～70 ℃, and reaction pressure is 0.01～0.8MPa, and reaction contact time is 1～100 second, C
1～C
4The ratio of the mole number of NO is 3～10: 1 among alkanol and the effluent I.C
1～C
4Alkanol is selected from methyl alcohol, ethanol or n-propyl alcohol, and preferred version is selected from methyl alcohol.Oxynitride makes from ammonia oxidation, nitric acid tail gas or nitrite and sulfuric acid reaction, and the oxynitride preferred version is selected from ammonia oxidation and makes.
Load silicon oxide, aluminum oxide, molecular sieve or inert filler in the technique scheme among the reactor II, also can load various Stainless Steel Helicess, main effect is fully to react for gas-liquid the place is provided, and quickens to conduct heat and mass transfer 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 modes of the residence time and oxynitride, oxygen and alcohol 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.Research process finds in surprise, oxynitride and oxygen at low temperatures, when especially being lower than 50 ℃, N in its product
2O
4Content can be up to more than 10%, but temperature is higher than after 100 ℃ N in its product
2O
4Content can be lower than 0.5%; But generally, therefore the esterification optimal temperature scope of alcohol and oxynitride, as if with oxygen, oxynitride (mainly being NO) and pure 30～60 ℃ of reactions, obviously, generates N between 30～60 ℃
2O
4Reaction probability height, and then nitric acid side reaction odds is big, the selectivity of nitrous acid ester reduces, but, if temperature of reaction is raise, the further oxidation of meeting causes the generation of side reactions such as aldehyde between the components such as oxygen and alcohol, can cause alkyl nitrite optionally to reduce equally.Based on above-mentioned analysis, the present invention adopts oxygen and oxynitride at high temperature to carry out catalyzed reaction earlier, at first generates NO and NO
2Mol ratio is greater than 1, and N
2O
4The oxynitride mixture that content is extremely low directly enters esterifier (reactor II) with this mixture and alcohol afterwards again, finishes esterification fast at lesser temps, respectively gets the chief, thereby has prevented N on the one hand
2O
4Generation, guaranteed again that on the other hand esterification carries out under preferable reaction conditions, finally both effectively prevented the generation of nitric acid, greatly improved the selectivity of nitrous acid ester again.
Adopt technical scheme of the present invention, allow oxynitride and oxygen at first enter reactor I, contact with aluminosilicate catalyst, reaction generates and contains NO
2Effluent I with unreacted NO; Effluent I and C
1～C
4Alkanol enters reactor II, and reaction generates and contains C
1～C
4The effluent II of alkyl nitrous acid ester; Contain C
1～C
4The effluent II of alkyl nitrous acid ester obtains C after separating
1～C
4The alkyl nitrous acid ester uses by entering the subsequent reactions unit after the drying treatment again; Wherein, 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, NO is 4～15: 1 with the ratio of the mole number of oxygen in the oxynitride.The temperature of reaction of reactor I is 121～170 ℃, and reaction pressure is 0.01～0.8MPa, and reaction contact time is 2～50 seconds, and the temperature of reaction of reactor II is 30～70 ℃, and reaction pressure is 0.01～0.8MPa, and reaction contact time is 1～100 second, C
1～C
4The ratio of the mole number of NO is C under 3～10: 1 the condition among alkanol and the effluent I
1～C
4The selectivity of alkyl nitrous acid ester is greater than 98%, and the content of nitric acid has been obtained better technical effect less than 5ppm.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Oxynitride and oxygen at first enter reactor I, are that 400: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, and NO is 6: 1 with the ratio of the mole number of oxygen, the temperature of reaction of reactor I is 80 ℃, reaction pressure is 0.01MPa, and reaction contact time is 2 seconds, and the temperature of reaction of reactor II is 30 ℃, reaction pressure is 0.01MPa, reaction contact time is 10 seconds, and the ratio of the mole number of NO is 3: 1 among methyl alcohol and the effluent I, among the reactor II under the condition of filling inertia aluminum oxide, its result is: the selectivity of methyl nitrite is 98.2%, and the content of nitric acid is 5ppm.
[embodiment 2]
Oxynitride and oxygen at first enter reactor I, are that 200: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, and NO is 4: 1 with the ratio of the mole number of oxygen, the temperature of reaction of reactor I is 121 ℃, reaction pressure is-0.05MPa, and reaction contact time is 60 seconds, and the temperature of reaction of reactor II is 80 ℃, reaction pressure is-0.05MPa, reaction contact time is 80 seconds, and the ratio of the mole number of NO is 9: 1 among methyl alcohol and the effluent I, among the reactor II under the condition of filling inertia silicon oxide, its result is: the selectivity of methyl nitrite is 98.8%, and the content of nitric acid is 3ppm.
[embodiment 3]
Oxynitride and oxygen at first enter reactor I, are that 50: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, and NO is 5: 1 with the ratio of the mole number of oxygen, the temperature of reaction of reactor I is 160 ℃, reaction pressure is 0.5MPa, and reaction contact time is 10 seconds, and the temperature of reaction of reactor II is 40 ℃, reaction pressure is 0.5MPa, reaction contact time is 20 seconds, and the ratio of the mole number of NO is 3.5: 1 among methyl alcohol and the effluent I, among the reactor II under the condition of filling 5A molecular sieve, its result is: the selectivity of methyl nitrite is 98.9%, and the content of nitric acid is 0.
[embodiment 4]
Oxynitride and oxygen at first enter reactor I, are that β-molecular sieve catalyst of 80: 1 contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO and NO
2Mixture, wherein NO and NO
2Mol ratio is 4: 1, and NO is 20: 1 with the ratio of the mole number of oxygen.The temperature of reaction of reactor I is 130 ℃, reaction pressure is 0.7MPa, reaction contact time is 3 seconds, the temperature of reaction of reactor II is 50 ℃, and reaction pressure is 0.7MPa, and reaction contact time is 5 seconds, the ratio of the mole number of NO is 4: 1 among methyl alcohol and the effluent I, under the condition of filling 4A molecular sieve, its result is: the selectivity of methyl nitrite is 99.2% among the reactor II, and the content of nitric acid is 0.
[embodiment 5]
Oxynitride and oxygen at first enter reactor I, are that β-molecular sieve catalyst of 100: 1 contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and ethanol enter reactor II, and reaction generates the effluent II that contains ethyl nitrite; The effluent II that contains ethyl nitrite obtains ethyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO and NO
2Mixture, wherein NO and NO
2Mol ratio is 6: 1, NO is 15: 1 with the ratio of the mole number of oxygen, and the temperature of reaction of reactor I is 110 ℃, and reaction pressure is 0.2MPa, reaction contact time is 1 second, the temperature of reaction of reactor II is 45 ℃, and reaction pressure is 0.2MPa, and reaction contact time is 30 seconds, the ratio of the mole number of NO is 5: 1 among ethanol and the effluent I, under the condition of filling ZSM-5 molecular sieve, its result is: the selectivity of ethyl nitrite is 99.0% among the reactor II, and the content of nitric acid is 0.
[embodiment 6]
Oxynitride and oxygen at first enter reactor I, are that 30: 1 y-zeolite catalyzer contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and propyl alcohol enter reactor II, and reaction generates the effluent II that contains propyl nitrite; The effluent II that contains propyl nitrite obtains propyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO and NO
2Mixture, wherein NO and NO
2Mol ratio is 3: 1, and NO is 5: 1 with the ratio of the mole number of oxygen.The temperature of reaction of reactor I is 130 ℃, reaction pressure is 0.3MPa, reaction contact time is 5 seconds, the temperature of reaction of reactor II is 30 ℃, and reaction pressure is 0.3MPa, and reaction contact time is 15 seconds, the ratio of the mole number of NO is 15: 1 among propyl alcohol and the effluent I, under the condition of filling inertia 5A molecular sieve, its result is: the selectivity of propyl nitrite is 99.3% among the reactor II, and the content of nitric acid is 0.
[embodiment 7]
Oxynitride and oxygen at first enter reactor I, are that 60: 1 MCM-22 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, NO
2And N
2O
3Mixture, wherein NO and NO
2And N
2O
3Mol ratio be 4: 1: 3, NO is 10: 1 with the ratio of the mole number of oxygen.The temperature of reaction of reactor I is 125 ℃, reaction pressure is 0.1MPa, reaction contact time is 1.8 seconds, the temperature of reaction of reactor II is 40 ℃, and reaction pressure is 0.3MPa, and reaction contact time is 8 seconds, the ratio of the mole number of NO is 12: 1 among methyl alcohol and the effluent I, under the condition of filling Stainless Steel Helices, its result is: the selectivity of methyl nitrite is 98.9% among the reactor II, and the content of nitric acid is 0.
[embodiment 8]
Oxynitride and oxygen at first enter reactor I, are that 200: 1 MCM-22 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO and N
2O
3Mixture, wherein NO and N
2O
3Mol ratio be 2: 1, NO is 15: 1 with the ratio of the mole number of oxygen, and the temperature of reaction of reactor I is 160 ℃, and reaction pressure is 0.6MPa, reaction contact time is 0.5 second, the temperature of reaction of reactor II is 38 ℃, and reaction pressure is 0.3MPa, and reaction contact time is 2 seconds, the ratio of the mole number of NO is 3.5: 1 among methyl alcohol and the effluent I, under the condition of filling inertia porcelain ring, its result is: the selectivity of methyl nitrite is 99.1% among the reactor II, and the content of nitric acid is 0.
[embodiment 9]
Oxynitride and oxygen at first enter reactor I, are that 10: 1 SAPO-34 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, and reaction generates the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, and NO is 4.5: 1 with the ratio of the mole number of oxygen, the temperature of reaction of reactor I is 90 ℃, reaction pressure is 0.1MPa, and reaction contact time is 3 seconds, and the temperature of reaction of reactor II is 42 ℃, reaction pressure is 0.3MPa, reaction contact time is 25 seconds, and the ratio of the mole number of NO is 3: 1 among methyl alcohol and the effluent I, among the reactor II under the condition of filling inert ceramic balls, its result is: the selectivity of methyl nitrite is 99.5%, and the content of nitric acid is 0.
[embodiment 10]
Oxynitride and oxygen at first enter reactor I, are that 800: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and ethanol enter reactor II, and reaction generates the effluent II that contains ethyl nitrite; The effluent II that contains ethyl nitrite obtains ethyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, and NO is 5: 1 with the ratio of the mole number of oxygen, the temperature of reaction of reactor I is 150 ℃, reaction pressure is-0.05MPa, and reaction contact time is 3 seconds, and the temperature of reaction of reactor II is 40 ℃, reaction pressure is-0.05MPa, reaction contact time is 10 seconds, and the ratio of the mole number of NO is 3.5: 1 among ethanol and the effluent I, among the reactor II under the condition of filling inertia aluminum oxide, its result is: the selectivity of ethyl nitrite is 99.2%, and the content of nitric acid is 0.
[embodiment 11]
Oxynitride and oxygen at first enter reactor I, are that 600: 1 ZSM-5 molecular sieve catalyst contacts with the Si/Al mol ratio, and reaction generates and contains NO
2And the effluent I of unreacted NO; Effluent I and ethanol enter reactor II, and reaction generates the effluent II that contains ethyl nitrite; The effluent II that contains ethyl nitrite obtains ethyl nitrite after separating, use by entering the subsequent reactions unit after the drying treatment again; Wherein, oxynitride is selected from NO, and NO is 7: 1 with the ratio of the mole number of oxygen, the temperature of reaction of reactor I is 140 ℃, reaction pressure is 0.5MPa, and reaction contact time is 8 seconds, and the temperature of reaction of reactor II is 45 ℃, reaction pressure is 0.5MPa, reaction contact time is 20 seconds, and the ratio of the mole number of NO is 8: 1 among ethanol and the effluent I, among the reactor II under the condition of filling inertia aluminum oxide, its result is: the selectivity of ethyl nitrite is 99.1%, and the content of nitric acid is 0.
[comparative example 1]
According to embodiment 8 identical catalyzer, condition and reaction raw materials, just there is not reactor I, its result is: the selectivity of methyl nitrite is 90.5%, the content of nitric acid is 1000ppm.
Claims (10)
1. one kind prepares C
1～C
4The method of alkyl nitrous acid ester comprises the steps:
A) oxynitride and oxygen at first enter reactor I, contact with aluminosilicate catalyst, and reaction generates and contains NO
2And the effluent I of unreacted NO;
B) effluent I and C
1～C
4Alkanol enters reactor II, and reaction generates and contains C
1～C
4The effluent II of alkyl nitrous acid ester;
C) contain C
1～C
4The effluent II of alkyl nitrous acid ester obtains C after separating
1～C
4The alkyl nitrous acid ester uses by entering the subsequent reactions unit after the drying treatment again;
Wherein, oxynitride is selected from NO, N
2O
3Or NO
2In one or more mixed gas, contain NO in the described oxynitride, the big NO of NO mole number
2Mole number; In the step a) in the oxynitride ratio of NO and the mole number of oxygen be 4～25: 1.
2. according to the described preparation of claim 1 C
1～C
4The method of alkyl nitrous acid ester is characterized in that: aluminosilicate catalyst is selected from least a among ZSM-5, β-molecular sieve, y-zeolite or the MCM-22, and its Si/Al mol ratio is 10～800: 1.
3. according to the described preparation of claim 2 C
1～C
4The method of alkyl nitrous acid ester is characterized in that: aluminosilicate catalyst is selected from ZSM-5, and its Si/Al mol ratio is 20～500: 1.
4. according to the described preparation of claim 1 C
1～C
4The method of alkyl nitrous acid ester is characterized in that: the temperature of reaction of reactor I is 40～180 ℃, and reaction pressure is-0.05～1.0MPa, and reaction contact time is 0.05～100 second, and NO is 4～20: 1 with the ratio of the mole number of oxygen in the oxynitride.
5. according to the described preparation of claim 4 C
1～C
4The method of alkyl nitrous acid ester is characterized in that: the temperature of reaction of reactor I is 121～170 ℃, and reaction pressure is 0.01～0.8MPa, and reaction contact time is 2～50 seconds, and NO is 4～15: 1 with the ratio of the mole number of oxygen in the oxynitride.
6. according to the described preparation of claim 1 C
1～C
4The method of alkyl nitrous acid ester, it is characterized in that: the temperature of reaction of reactor II is 20～100 ℃, reaction pressure is-0.05～1.0MPa, and reaction contact time is 0.05～200 second, and the ratio of the mole number of NO is 2～15: 1 among C1～C4 alkanol and the effluent I.
7. according to the described preparation of claim 6 C
1～C
4The method of alkyl nitrous acid ester is characterized in that: the temperature of reaction of reactor II is 30～70 ℃, and reaction pressure is 0.01～0.8MPa, and reaction contact time is 1～100 second, C
1～C
4The ratio of the mole number of NO is 3～10: 1 among alkanol and the effluent I.
8. according to the described preparation of claim 1 C
1～C
4The method of alkyl nitrous acid ester is characterized in that: C
1～C
4Alkanol is selected from methyl alcohol, ethanol or n-propyl alcohol.
9. according to the described preparation of claim 1 C
1～C
4The method of alkyl nitrous acid ester is characterized in that oxynitride makes from ammonia oxidation, nitric acid tail gas or nitrite and sulfuric acid reaction.
10. according to the described preparation of claim 9 C
1～C
4The method of alkyl nitrous acid ester is characterized in that loading among the reactor II silicon oxide, aluminum oxide, molecular sieve or inert filler.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924282A (en) * | 2012-11-30 | 2013-02-13 | 西南化工研究设计院有限公司 | Process for producing alkyl nitrite |
| CN104447344A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for producing alkyl nitrate |
| CN112142600A (en) * | 2019-06-27 | 2020-12-29 | 中国科学院大连化学物理研究所 | Preparation method and application of methyl nitrite |
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| CN112142600A (en) * | 2019-06-27 | 2020-12-29 | 中国科学院大连化学物理研究所 | Preparation method and application of methyl nitrite |
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