CN102649764B - Method for preparing C1-C4 alkyl nitrous acid ester by catalytic reaction - Google Patents
Method for preparing C1-C4 alkyl nitrous acid ester by catalytic reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing C1-C4 alkyl nitrous acid ester by a catalytic reaction, which mainly solves the problem in the prior art that a product, namely nitrous acid ester is low in selectivity. The method comprises the following steps: (a), a nitrogen oxide and oxygen enter a reactor I and are in contact reaction with each other, so as to generate an effluence I containing NO2 and unreacted NO; (b), the effluence I and the C1-C4 alkanol enter a reactor II and are in contact reaction with a resin catalyst so as to generate an effluence II containing nitrous acid ester; and (c), the nitrous acid ester is obtained through separating the effluence II, wherein the reactor I is a fixed bed reactor, the reactor II is a revolving bed high-gravity field reactor, and a resin catalyst layer is fixed on the rotor of the revolving bed high-gravity field reactor. According to the invention, the problem is better solved, and the method is suitable for the industrial production of increasing yield of the C1-C4 alkyl nitrous acid ester.
Description
Technical field
The present invention relates to a kind of catalyzed reaction and produce C
1～C
4the method of alkyl nitriteester, particularly about the required C of CO coupling producing oxalic ester
1～C
4the production method of alkyl nitriteester.
Background technology
Barkite is important Organic Chemicals, in a large number produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate for fine chemistry industry.Enter 21 century, barkite is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, barkite ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example, carry 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 is pharmaceutically used as hormone.In addition, barkite low-voltage hydrogenation can be produced very important 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, 2007 years nearly 4,800,000 tons of import volumes.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and production technique cost is high, and energy consumption is large, seriously polluted, and prepared using is unreasonable.For many years, people are finding an operational path that cost is low, environment is good always.The sixties in last century, the D.F.Fenton of Associated Oil Company of the U.S. finds, carbon monoxide, alcohol and oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and ARCO company of the U.S. have carried out research and development in succession in this field since then.
Divide and can be divided into liquid phase method and vapor phase process from development course for Oxidation of Carbon Monoxide coupling method synthesis of oxalate.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is harsher, and reaction is under high pressure carried out, liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.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 technique of Yu Buxingchan company 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)
Be to make the high efficiency reasonable use of NO, RONO, ROH highly selective in two-step reaction process by the key problem in technology of known this system of said process.
But; practical situation are in the reaction process of step (2); except generating principal product alkyl nitriteester; also often having side reaction occurs; especially there is the rare nitric acid of by product to generate; this must consume more NO gas, increases energy consumption and cost, also can bring equipment corrosion etc. simultaneously.Although, more about how producing the document of alkyl nitriteester, about how effectively improving the selectivity of alkyl nitrite, better prevent that the report that nitric acid side reaction occurs 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 supported catalyst, coupling oxalic diethyl ester crude product, reaction is self-closing circulating process, CO gas enters coupler reactor with the ethyl nitrite from regeneration reactor through mixing preheating, after reaction, gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, non-condensable gas containing 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, test is found in the method, in regeneration reactor, the selectivity of ethyl nitrite is 90% left and right.
In above-mentioned document, in regeneration reactor, there is the low shortcoming of selectivity that generates nitrous acid ester.
High-gravity technology is the new technology of strengthening polyphasic flow transmission and reaction process, since eighties of last century is come out, at home and abroad paid attention to widely, due to it broad applicability and have that the volume that legacy equipment do not have is little, lightweight, energy consumption is low, easy running, easy-maintaining, safety, the advantage such as can conform reliably, flexibly and more, make high-gravity technology have wide commercial applications prospect in the industrial circles such as environmental protection and material biochemical industry.But at present high-gravity technology is also mainly in the application and development stage, and rotating bed super gravity field reactor is applied to C
1～C
4in the production of alkyl nitriteester, have not been reported.
Summary of the invention
Technical problem to be solved by this invention is the C existing in previous literature
1～C
4the technical problem that alkyl nitriteester selectivity is low, provides a kind of new catalyzed reaction to produce C
1～C
4the method of alkyl nitriteester.The method has C
1～C
4the advantage that alkyl nitriteester 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 catalyzed reaction is produced C
1～C
4the method of alkyl nitriteester, comprises the steps:
A) first oxynitride and oxygen 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, generates and contains C with resin catalyst contact reacts
1～C
4the effluent II of alkyl nitriteester;
C) contain C
1～C
4the effluent II of alkyl nitriteester obtains C after separating
1～C
4alkyl nitriteester;
Wherein, reactor I is fixed-bed reactor, and reactor II is rotating bed super gravity field reactor, is fixed with resin catalyst layer on the rotor of rotating bed super gravity field reactor; Oxynitride is selected from NO, N
2o
3or NO
2in one or more mixed gas, in described oxynitride, contain NO, the large NO of NO mole number
2mole number; Step a) in oxynitride NO be 4～25: 1 with the ratio of the mole number of oxygen.
In technique scheme, aluminosilicate catalyst preferred version is selected from least one in ZSM-5, β-molecular sieve, y-zeolite or 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; Resin catalyst is preferably selected from acidic ion exchange resin.
In technique scheme, the reaction conditions of reactor I is: 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 oxynitride is 4～20: 1 with the ratio preferable range of the mole number of oxygen.The preferred reaction conditions of reactor I is: 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 oxynitride the 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 ℃.
In technique scheme, the reaction conditions of reactor II is: temperature of reaction is 10～100 ℃, and reaction pressure is-0.05～1.0MPa, and in C1～C4 alkanol and effluent I, the ratio of the mole number of NO is 1～15: 1.The preferred reaction conditions of reactor II is: temperature of reaction is 20～70 ℃, and reaction pressure is 0.01～0.8MPa, C
1～C
4in alkanol and effluent I, the ratio of the mole number of NO is 1～10: 1.C
1～C
4alkanol is selected from methyl alcohol, ethanol or n-propyl alcohol, and preferred version is selected from methyl alcohol.The rotating speed of the rotor of rotating bed super gravity field reactor is 100～5000rpm, and preferably speed range is 300～3000rpm.
As everyone knows, on the earth, all substances are all because gravity is by earth attraction, 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 the new technology of strengthening polyphasic flow transmission and reaction process, since eighties of last century is come out, at home and abroad paid attention to widely, due to it broad applicability and have that the volume that legacy equipment do not have is little, lightweight, energy consumption is low, easy running, easy-maintaining, safety, the advantage such as can conform reliably, flexibly and more, make high-gravity technology have wide commercial applications prospect in the industrial circles such as environmental protection and material biochemical industry.But high-gravity technology, also mainly in the application and development stage, embodies a concentrated reflection of the gas-solid fluidization technology of hypergravity and two aspects of hypergravity gas-liquid mass transferring technology at present.
Under the Elevated Gravity of large hundreds of times to thousand times than earth gravity field, huge shearing force is torn into liquid liquid film, brin, the drop of micron to nano grade, produce huge, the quick phase interface upgrading, greatly increase gas-to-liquid contact specific surface area, make 1～3 order of magnitude of raising in 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.
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 conventionally.Its principle of work be gas phase through gas inlet tube by tangentially 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 shower nozzle sprinkle on rotor inner edge.The liquid that enters rotor is subject to the effect of filler (catalyzer) in rotor, and circumferential speed increases, and the centrifugal force producing pushes it against rotor outer rim.In this process, the surface-area that liquid is become greatly, constantly updates by fillers dispersed, crushing-type, tortuous runner has aggravated the renewal of fluid surface.Like this, fabulous mass transfer and reaction conditions have been formed at internal rotor.Liquid leaves overweight machine through liquid outlet tube after being thrown shell and collect by rotor.Gas leaves rotor from rotor center, is drawn by gas outlet tube, completes mass transfer and reaction process.
Research shows, 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 etc. all makes a significant impact the selectivity of nitrous acid ester, and especially in the generation of nitric acid side reaction and raw material, oxynitride generates N
2o
4reaction have substantial connection, prevent N
2o
4generation be key problem in technology.Research process finds in surprise, oxynitride and oxygen at low temperatures, during especially 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, under normal circumstances, the esterification optimal temperature scope of alcohol and oxynitride between 30～60 ℃, therefore, if by oxygen, oxynitride (being mainly NO) and alcohol 30～60 ℃ of reactions, obviously, generate N
2o
4reaction probability high, and then nitric acid side reaction odds is large, the elective reduction of nitrous acid ester, but, if temperature of reaction is raise, between the components such as oxygen and alcohol, can further be oxidized the generation that causes the side reactions such as aldehyde, can cause equally alkyl nitrite optionally to reduce.Based on above-mentioned analysis, the present invention adopts oxygen and oxynitride at high temperature first to carry out catalyzed reaction, 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) by this mixture and alcohol afterwards again.Research also finds that it is fast response that oxynitride generates reacting of alkyl nitrite with oxygen and alcohol generation oxidative esterification, and the reaction of side reaction generation nitric acid etc. is slightly slow, the speed of reaction of NO oxidative esterification reaction process is mainly subject to the impact of gas-liquid resistance to mass transfer, if effectively improve gas-liquid mass transfer efficiency, can further effectively reduce N
2o
4generation probability, further prevent the generation of the side reactions such as nitric acid, technical solution of the present invention is fully being studied on the basis of feature of oxynitride and oxygen and alcohol generation oxidative esterification reaction, propose to adopt again the rotating bed super gravity field reactor of loaded resin catalyzer, as oxidative esterification reaction device, 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 promoter action of resin catalyst to oxidative esterification reaction, and then more effectively promote main reaction, the draw up generation of side reaction of the degree of depth, thereby improve the utilization ratio of the raw materials such as NO, greatly improve the selectivity of nitrous acid ester.
Adopt technical scheme of the present invention, allow oxynitride and oxygen 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, generates and contains C with resin catalyst contact reacts
1～C
4the effluent II of alkyl nitriteester; Contain C
1～C
4the effluent II of alkyl nitriteester obtains C after separating
1～C
4alkyl nitriteester; Wherein, reactor I is fixed-bed reactor, and reactor II is rotating bed super gravity field reactor, is fixed with resin catalyst layer on the rotor of rotating bed super gravity field reactor; Oxynitride is selected from NO, N
2o
3or NO
2in one or more mixed gas, in described oxynitride, contain NO, NO mole number is greater than NO
2mole number, in oxynitride, NO is 4～15: 1 with the ratio of the mole number of oxygen.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, the temperature of reaction of reactor II is 20～70 ℃, reaction pressure is 0.01～0.8MPa, and the rotating speed of the rotor of rotating bed super gravity reactor is 300～3000rpm, C
1～C
4in alkanol and effluent I, the ratio of the mole number of NO is under 1～10: 1 condition, C
1～C
4the selectivity of alkyl nitriteester is greater than 99%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
First oxynitride and oxygen enter reactor I, and the ZSM-5 molecular sieve catalyzer that is 280: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board 002CR type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and this reactor, with rotating bed super gravity field reactor in embodiment 1 in patent CN1895766A identical (as follows), is just filled with resin catalyst on rotor; Oxynitride is selected from NO, 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 3 seconds, and the temperature of reaction of reactor II is 30 ℃, reaction pressure is 0.01MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 3: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 1000rpm, its result is: the selectivity of methyl nitrite is 99.73%.
[embodiment 2]
First oxynitride and oxygen enter reactor I, and the ZSM-5 molecular sieve catalyzer that is 200: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board 002CR type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, oxynitride is selected from NO, 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, reaction contact time is 60 seconds, the temperature of reaction of reactor II is 80 ℃, reaction pressure is-0.05MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 9: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 800rpm, its result is: the selectivity of methyl nitrite is 99.81%.
[embodiment 3]
First oxynitride and oxygen enter reactor I, and the ZSM-5 molecular sieve catalyzer that is 50: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board 002CR type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, oxynitride is selected from NO, 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, reaction contact time is 10 seconds, the temperature of reaction of reactor II is 40 ℃, reaction pressure is 0.5MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 3.5: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 2000rpm, its result is: the selectivity of methyl nitrite is 99.58%.
[embodiment 4]
First oxynitride and oxygen enter reactor I, and the β-molecular sieve catalyst that is 80: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board 005CR type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and 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 ℃, reaction pressure is 0.7MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 4: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 3000rpm, its result is: the selectivity of methyl nitrite is 99.66%.
[embodiment 5]
First oxynitride and oxygen enter reactor I, and the β-molecular sieve catalyst that is 100: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and ethanol enter reactor II, generate with Su Qing board 005CR type resin catalyst contact reacts the effluent II that contains ethyl nitrite; The effluent II that contains ethyl nitrite obtains ethyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and 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, the temperature of reaction of reactor I is 110 ℃, reaction pressure is 0.2MPa, and reaction contact time is 1 second, and the temperature of reaction of reactor II is 45 ℃, reaction pressure is 0.2MPa, in ethanol and effluent I, the ratio of the mole number of NO is 5: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 4000rpm, its result is: the selectivity of ethyl nitrite is 99.95%.
[embodiment 6]
First oxynitride and oxygen enter reactor I, and the y-zeolite catalyzer that is 30: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and propyl alcohol enter reactor II, generate with Su Qing board D006 type resin catalyst contact reacts the effluent II that contains propyl nitrite; The effluent II that contains propyl nitrite obtains propyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and 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 ℃, reaction pressure is 0.3MPa, in propyl alcohol and effluent I, the ratio of the mole number of NO is 15: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 4800rpm, its result is: the selectivity of propyl nitrite is 99.96%.
[embodiment 7]
First oxynitride and oxygen enter reactor I, and the MCM-22 molecular sieve catalyst that is 60: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board D006 type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and 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 ℃, reaction pressure is 0.3MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 12: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 1500rpm, its result is: the selectivity of methyl nitrite is 99.88%.
[embodiment 8]
First oxynitride and oxygen enter reactor I, and the MCM-22 molecular sieve catalyst that is 200: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board D002 type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and 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, the temperature of reaction of reactor I is 160 ℃, reaction pressure is 0.6MPa, and reaction contact time is 0.5 second, and the temperature of reaction of reactor II is 38 ℃, reaction pressure is 0.3MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 3.5: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 2500rpm, its result is: the selectivity of methyl nitrite is 99.83%.
[embodiment 9]
First oxynitride and oxygen enter reactor I, and the SAPO-34 molecular sieve catalyst that is 10: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and methyl alcohol enter reactor II, generate with Su Qing board D002-II type resin catalyst contact reacts the effluent II that contains methyl nitrite; The effluent II that contains methyl nitrite obtains methyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, oxynitride is selected from NO, 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, reaction contact time is 3 seconds, the temperature of reaction of reactor II is 42 ℃, reaction pressure is 0.3MPa, in methyl alcohol and effluent I, the ratio of the mole number of NO is 3: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 1800rpm, its result is: the selectivity of methyl nitrite is 99.89%.
[embodiment 10]
First oxynitride and oxygen enter reactor I, and the ZSM-5 molecular sieve catalyzer that is 800: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and ethanol enter reactor II, generate with Su Qing board D002-II type resin catalyst contact reacts the effluent II that contains ethyl nitrite; The effluent II that contains ethyl nitrite obtains ethyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, oxynitride is selected from NO, 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, reaction contact time is 3 seconds, the temperature of reaction of reactor II is 20 ℃, reaction pressure is-0.05MPa, in ethanol and effluent I, the ratio of the mole number of NO is 3.5: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 3000rpm, its result is: the selectivity of ethyl nitrite is 99.91%.
[embodiment 11]
First oxynitride and oxygen enter reactor I, and the ZSM-5 molecular sieve catalyzer that is 600: 1 with Si/Al mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and ethanol enter reactor II, generate with Su Qing board D002 type resin catalyst contact reacts the effluent II that contains ethyl nitrite; The effluent II that contains ethyl nitrite obtains ethyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, oxynitride is selected from NO, 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, reaction contact time is 8 seconds, the temperature of reaction of reactor II is 15 ℃, reaction pressure is 0.5MPa, in ethanol and effluent I, the ratio of the mole number of NO is 8: 1, and under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 600rpm, its result is: the selectivity of ethyl nitrite is 99.92%.
[comparative example 1]
According to the identical condition of embodiment 8 and reaction raw materials, just in reactor II, there is no loaded resin catalyzer, its result is: the selectivity of methyl nitrite is 96.1%.
[comparative example 2]
According to the identical condition of embodiment 8 and reaction raw materials, just reactor II adopts fixed-bed reactor, and its result is: the selectivity of methyl nitrite is 93.1%.
Claims (1)
1. catalyzed reaction is produced a method for propyl nitrite, and step is:
First oxynitride and oxygen enter reactor I, and the y-zeolite catalyzer that is 30:1 with Si/A1 mol ratio contacts, and reaction generates and contains NO
2and the effluent I of unreacted NO; Effluent I and propyl alcohol enter reactor II, generate with Su Qing board D006 type resin catalyst contact reacts the effluent II that contains propyl nitrite; The effluent II that contains propyl nitrite obtains propyl nitrite after separating; Wherein, reactor II is rotating bed super gravity field reactor, and 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 ℃, reaction pressure is 0.3MPa, in propyl alcohol and effluent I, the ratio of the mole number of NO is 15:1, under the condition that in reactor II, the rotating speed of the rotor of rotating bed super gravity reactor is 4800rpm; Wherein, reactor I is fixed-bed reactor, and reaction result is: the selectivity of propyl nitrite is 99.96%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4879401A (en) * | 1987-09-29 | 1989-11-07 | Union Carbide Chemicals And Plastics Company Inc. | Process for removal of impurities in alkyl nitrite formation |
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| CN1151334A (en) * | 1995-12-02 | 1997-06-11 | 中国石化齐鲁石油化工公司 | Method for prepn. of catalyst of large porous strong acid cation exchange resin |
| CN1611293A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Ultragravity field rotary bed mass transfer and conversion unit |
| CN101096340A (en) * | 2006-06-27 | 2008-01-02 | 上海焦化有限公司 | Process for the preparation of C1-C4-alkyl nitrites |
| CN101259368A (en) * | 2008-04-11 | 2008-09-10 | 浙江工业大学 | Method for catalytic oxidation NO with ZSM-5 type molecular sieve as catalyst |
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