CN102219696B - Method for preparing C1-C4 alkyl nitrite - Google Patents
Method for preparing C1-C4 alkyl nitrite Download PDFInfo
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- CN102219696B CN102219696B CN201010146997.3A CN201010146997A CN102219696B CN 102219696 B CN102219696 B CN 102219696B CN 201010146997 A CN201010146997 A CN 201010146997A CN 102219696 B CN102219696 B CN 102219696B
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Abstract
The invention relates to a method for preparing C1-C4 alkyl nitrite, and the method is mainly used for solving the technical problems that the selectivity of a target product is low and the content of nitric acid in a side reaction product is high in the prior art. The method comprises the step: based on nitrogen oxide, oxygen and C1-C4 alkanol serving as raw materials and a rotating bed super-gravity field device serving as a reactor, carrying out contact reaction on the raw materials in the rotating bed super-gravity field device at the reaction temperature of 0-150 DEG C at the reaction pressure of minus 0.009-1.5 MPa based on the condition that the molar ratio of C1-C4 alkanol to nitrogen oxide is (1-100):1 and the molar ratio of nitrogen oxide to oxygen is (4-50):1, thus generating effluent containing C1-C4 alkyl nitrite. By utilizing the technical scheme of the invention, the problems in the prior art are well solved. The method can be used in industrial production for increasing the yield of the C1-C4 alkyl nitrite.
Description
Technical field
The present invention relates to a kind of C of preparation
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 for fine chemistry industry, produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.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 pharmaceutically as the chest acyl alkali of hormone.In addition, barkite low-voltage hydrogenation can be prepared very important industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost compare Gao， China needs a large amount of import ethylene glycol every year, and within 2007 years, import volume is nearly 4,800,000 tons.
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 U.S. Associated Oil Company 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 U.S. ARCO company have carried out research and development in succession in this field since then.
For Oxidation of Carbon Monoxide coupling method synthesis of oxalate, from development course, divide and can be divided into liquid phase method and vapor phase process.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)
Key problem in technology by known this system of said process is to make the high efficiency reasonable use of NO, RONO, ROH highly selective in two-step reaction process.
But practical situation are in the reaction process of step (2), except generating principal product alkyl nitriteester; also often have side reaction and occur, especially have the rare nitric acid of by product to generate, this must consume more NO gas; increase energy consumption and cost, also can bring equipment corrosion etc. simultaneously.Although relevant document how to produce alkyl nitriteester is more, the relevant selectivity that how effectively to improve alkyl nitrite, better prevents that 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 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, in the present invention, do not mention the selectivity of ethyl nitrite.
Document CN 95116136.9 discloses the catalyzer of the synthetic use of a kind of barkite, selects Zr to make auxiliary agent, by pickling process, develops novel Pd-Zr/Al
2o
3catalyzer.It is to adopt fixed-bed reactor that this catalyzer reacts with nitrous acid ester synthesis of oxalic ester by gaseous catalysis as carbon monoxide.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, mentions rotating bed and can be used for the 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 oil-field flooding deoxidation; CN1116146A discloses a kind of method of preparing ultrafine particle under super gravity field.
Super gravity field technology is the new technology that early eighties just occurs, its internal mechanism is also continuing exploration, and research for application and development is still constantly being carried out, and new Application Areas, also in continuous developing, is also applied to C about rotating bed for now
1～C
4the report that alkyl nitriteester is produced.
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, side reaction product nitric acid content is high, provides a kind of new preparation C
1～C
4the method of alkyl nitriteester.The method has C
1～C
4the advantage that alkyl nitriteester selectivity is high, 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 C for preparing
1～C
4the method of alkyl nitriteester, with oxynitride, oxygen and C
1～C
4alkanol is raw material, utilizes rotating bed super gravity field device as reactor, in temperature of reaction, is 0～150 ℃, 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 that under 4～50: 1 condition, raw material is contact reacts in rotating bed super gravity field device with the ratio of the mole number of oxygen, generates and contains C
1～C
4the effluent of alkyl nitriteester.
In technique scheme, on the rotor of rotating bed super gravity field device, be fixed with protruded packing layer; Oxynitride, oxygen and C in raw material
1～C
4alkanol with adverse current, and stream or the mode of cross-flow by protruded packing layer.
In technique scheme, oxynitride is preferably 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 rotating bed super gravity field device, reaction conditions preferable range is: temperature of reaction is 10～100 ℃, 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 4～20: 1 with the ratio of the mole number of oxygen; Reaction conditions more preferably scope is: temperature of reaction is 10～60 ℃, and reaction pressure is-0.05～0.8MPa, C
1～C
4alkanol is 1～20: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～10: 1 with the ratio of the mole number of oxygen.
In technique scheme, the rotating speed of the rotor of rotating bed super gravity field device is 100～5000rpm, and preferably speed range is 300～3000rpm.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, 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 phase interface huge, that upgrade fast, greatly increased 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 comprised 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, by rotor outer rim place, enter filler.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 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, at internal rotor, fabulous mass transfer and reaction conditions have been formed.Liquid is thrown shell by rotor and is collected by liquid outlet tube and leave overweight machine.Gas leaves rotor from rotor center, by gas outlet tube, is drawn, and 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 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 effectively reduce N
2o
4generation probability, and then prevent the generation of the side reactions such as nitric acid; Technical solution of the present invention is on the basis of feature of fully studying oxynitride and oxygen and alcohol generation oxidative esterification reaction, propose to adopt rotating bed super gravity field device as reactor, 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 then effectively promote main reaction, the draw up generation of side reaction, thereby improve the utilization ratio of the raw materials such as NO, greatly improved the selectivity of nitrous acid ester.
Adopt technical scheme of the present invention, with oxynitride, oxygen and C
1～C
4alkanol is raw material, utilizes rotating bed super gravity field device as reactor, in temperature of reaction, is 10～60 ℃, and reaction pressure is-0.05～0.8MPa, C
1～C
4alkanol is 1～20: 1 with the ratio of the mole number of oxynitride, oxynitride is 4～10: 1 with the ratio of the mole number of oxygen, the rotating speed of the rotor of rotating bed super gravity field device is under 300～3000rpm condition, and raw material is contact reacts in rotating bed super gravity field device, generates and contains C
1～C
4the effluent of alkyl nitriteester, wherein C
1～C
4the selectivity of alkyl nitriteester can be 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]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field reactor, this reactor is with rotating bed super gravity field device reaction device in embodiment 1 in patent CN1895766A identical (following identical), oxynitride is selected from NO, NO is 6: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 10 ℃, reaction pressure is-0.08MPa, methyl alcohol is 2: 1 with the ratio of the mole number of NO, the rotating speed of the rotor of rotating bed super gravity field device is under 500rpm condition, raw material is contact reacts in rotating bed super gravity field device, its result is: the transformation efficiency 100% of oxygen, the selectivity of methyl nitrite is 99.25%.
[embodiment 2]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, oxynitride is selected from NO, NO is 5: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 30 ℃, reaction pressure is-0.05MPa, and methyl alcohol is 1.5: 1 with the ratio of the mole number of NO, and the rotating speed of the rotor of rotating bed super gravity field device is under 1000rpm condition, raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.51%.
[embodiment 3]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, oxynitride is selected from NO, NO is 8: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 50 ℃, reaction pressure is-0.02MPa, and methyl alcohol is 20: 1 with the ratio of the mole number of NO, and the rotating speed of the rotor of rotating bed super gravity field device is under 3000rpm condition, raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.43%.
[embodiment 4]
Oxynitride, oxygen and butanols also flow to into rotating bed super gravity field device reaction device, oxynitride is selected from NO, NO is 20: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 120 ℃, reaction pressure is 1.2MPa, and butanols is 5: 1 with the ratio of the mole number of NO, and the rotating speed of the rotor of rotating bed super gravity field device is under 1500rpm condition, raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of butyl nitrite is 99.12%.
[embodiment 5]
Oxynitride, oxygen and butanols also flow to into rotating bed super gravity field device reaction device, and oxynitride is selected from NO and NO
2the mol ratio mixture that is 4: 1, NO is 4: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 100 ℃, reaction pressure is 0.8MPa, butanols is 3: 1 with the ratio of the mole number of NO, the rotating speed of the rotor of rotating bed super gravity field device is under 2000rpm condition, and raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of butyl nitrite is 99.18%.
[embodiment 6]
Oxynitride, oxygen and propyl alcohol cross-flow enter rotating bed super gravity field device reaction device, and oxynitride is selected from NO and NO
2the mol ratio mixture that is 3: 1, NO is 4: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 60 ℃, reaction pressure is 0.5MPa, propyl alcohol is 10: 1 with the ratio of the mole number of NO, the rotating speed of the rotor of rotating bed super gravity field device is under 1000rpm condition, and raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of propyl nitrite is 99.56%.
[embodiment 7]
Oxynitride, oxygen and ethanol adverse current enter rotating bed super gravity field device reaction device, oxynitride is selected from NO, NO is 4.5: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 40 ℃, reaction pressure is 0.05MPa, and ethanol is 1.2: 1 with the ratio of the mole number of NO, and the rotating speed of the rotor of rotating bed super gravity field device is under 4000rpm condition, raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of ethyl nitrite is 99.68%.
[embodiment 8]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, and oxynitride is selected from NO and NO
2the mol ratio mixture that is 2: 1, NO is 10: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 50 ℃, reaction pressure is 0.2MPa, methyl alcohol is 1.5: 1 with the ratio of the mole number of NO, the rotating speed of the rotor of rotating bed super gravity field device is under 3000rpm condition, and raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.87%.
[embodiment 9]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, and oxynitride is selected from NO and NO
2the mol ratio mixture that is 2: 1, NO is 20: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 30 ℃, reaction pressure is 0.06MPa, methyl alcohol is 10: 1 with the ratio of the mole number of NO, the rotating speed of the rotor of rotating bed super gravity field device is under 1000rpm condition, and raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.59%.
[embodiment 10]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, oxynitride is selected from NO, NO is 4.5: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 5 ℃, reaction pressure is-0.02MPa, and methyl alcohol is 1.5: 1 with the ratio of the mole number of NO, and the rotating speed of the rotor of rotating bed super gravity field device is under 800rpm condition, raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.49%.
[embodiment 11]
Oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, oxynitride is selected from NO, NO is 5: 1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 40 ℃, reaction pressure is 0.01MPa, and methyl alcohol is 1.5: 1 with the ratio of the mole number of NO, and the rotating speed of the rotor of rotating bed super gravity field device is under 2500rpm condition, raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.83%.
[comparative example 1]
According to the identical condition of embodiment 8 and reaction raw materials, just adopt fixed-bed reactor, its result is: the selectivity of methyl nitrite is 85.5%.
Claims (1)
1. a method of preparing methyl nitrite, oxynitride, oxygen and methyl alcohol adverse current enter rotating bed super gravity field device reaction device, and oxynitride is selected from NO and NO
2the mol ratio mixture that is 2:1, NO is 10:1 with the ratio of the mole number of oxygen, in temperature of reaction, it is 50 ℃, reaction pressure is 0.2MPa, methyl alcohol is 1.5:1 with the ratio of the mole number of NO, the rotating speed of the rotor of rotating bed super gravity field device is under 3000rpm condition, and raw material is contact reacts in rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.87%.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010146997.3A CN102219696B (en) | 2010-04-15 | 2010-04-15 | Method for preparing C1-C4 alkyl nitrite |
| US13/088,253 US8722918B2 (en) | 2010-04-15 | 2011-04-15 | Process for producing Cl-C4 alkyl nitrite |
| RU2011114842/04A RU2564028C2 (en) | 2010-04-15 | 2011-04-15 | Production of alkyl nitrite c1-c4 |
| AU2011201724A AU2011201724B2 (en) | 2010-04-15 | 2011-04-15 | A process for producing C1-C4 alkyl nitrite |
| JP2011090875A JP6027723B2 (en) | 2010-04-15 | 2011-04-15 | Method for producing C1-C4 alkyl nitrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010146997.3A CN102219696B (en) | 2010-04-15 | 2010-04-15 | Method for preparing C1-C4 alkyl nitrite |
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| Publication Number | Publication Date |
|---|---|
| CN102219696A CN102219696A (en) | 2011-10-19 |
| CN102219696B true CN102219696B (en) | 2014-01-22 |
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