CN102276472B - Method for producing C1-C4 alkyl nitrite - Google Patents
Method for producing C1-C4 alkyl nitrite Download PDFInfo
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- CN102276472B CN102276472B CN2010101999414A CN201010199941A CN102276472B CN 102276472 B CN102276472 B CN 102276472B CN 2010101999414 A CN2010101999414 A CN 2010101999414A CN 201010199941 A CN201010199941 A CN 201010199941A CN 102276472 B CN102276472 B CN 102276472B
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Abstract
The invention relates to a method for producing C1-C4 alkyl nitrite, which is used for mainly solving the technical problem of low objective product selectivity in the prior art. In the technical scheme of the method disclosed by the invention, nitrite, inorganic acid and C1-C4 alkanol are used as raw materials; water is used as diluents; a rotary bed super-gravity field device is used as a reactor; and the raw materials are in contact reaction in the rotary bed super-gravity field device at 0-120 DEG C with the reaction pressure of -0.09-15 MPa and the contact time of 0.01-50 s so that effluence containing C1-C4 alkyl nitrite is generated. The problem is solved better. The method can be applied to the industrial production of increasing production of the C1-C4 alkyl nitrite.
Description
Technical field
The present invention relates to a kind of production C
1~C
4The method of alkyl nitriteester, particularly about the required C of CO coupling producing oxalic ester
1~C
4The replenishing 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, the 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 with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds, carries out various condensation reactions.It can also synthesize pharmaceutically as the chest acyl alkali of hormone.In addition, the barkite low-voltage hydrogenation can be produced very important industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to produce at present, and cost is higher, and 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, with alcohol, esterification occurs and produces, and the 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.
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, the 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 emerging product company of space section 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)
From said process; theoretically; this reaction process is not consume NO, and still, practical situation are in the reaction process of step (2); except generating the principal product alkyl nitriteester; also often have side reaction and occur, especially have by product nitric acid to generate, this must consume more NO gas; need to supplement oxynitride in system, as NO or nitrous acid ester etc. for this reason.
Patent CN1772600A discloses the production method of the NO gas that a kind of synthesis of oxalate uses, the oxynitride that this production method directly generates with the air ammonia oxidation is used as the NO gas that synthesis of oxalate is used, perhaps directly with the oxynitride in nitric acid industry tail gas, be used as the NO gas that synthesis of oxalate is used, and adopt alcohols to absorb nitrous acid ester, and the method that adopts compression and condensation to combine fully reclaims alcohols and the nitrous acid ester in emission.Wherein ammonia is liquid ammonia or gaseous ammonia, and the concentration of its ammonia is 1~30V%; Oxygen is airborne oxygen or liquid oxygen or gaseous oxygen, and the concentration of its oxygen is at 1~30V%; Alcohols is methyl alcohol or ethanol or propyl alcohol or butanols, and its pure concentration is at 50~100wt%; Pressure used is 0.1~10MPa, and condensing temperature used is at-20 ℃~100 ℃.The shortcomings such as the production method of this oxynitride is the flow process complexity on the one hand, and operation energy consumption is high, simultaneously, in the oxynitride process of using at the production synthesis of oxalate, exists selectivity low, and side reaction is many, and raw material availability is low.
The EP0023745A3 patent that Britain Imperial Chemical Industries (ICI) propose, mention rotating bed and can be used for the processes such as absorption, parsing, distillation, but do 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 of producing ultrafine particle under super gravity field.
The 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, also is applied to C about rotating bed for now
1~C
4The report that alkyl nitriteester is produced.Especially about nitrite, mineral acid and C1~C4 alkyl alcohol reaction, do not produce C
1~C
4Alkyl nitriteester adopts the report of high-gravity technology.
Summary of the invention
Technical problem to be solved by this invention is the C existed in previous literature
1~C
4The technical problem that the alkyl nitriteester selectivity is low, provide a kind of new production C
1~C
4The method of alkyl nitriteester.The method has C
1~C
4The advantage that the 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 production C
1~C
4The method of alkyl nitriteester, with nitrite, mineral acid and C
1~C
4Alkanol is raw material, and water is thinner, usings the rotating bed super gravity field device as reactor, in temperature of reaction, be 0~120 ℃, reaction pressure is-0.09~1.5MPa, under the condition that be 0.01~50 second duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generates and contains C
1~C
4The effluent of alkyl nitriteester.
In technique scheme, the preferred molar ratio scope of water and nitrite is 1~20: 1, and more preferably molar ratio range is 1.2~10: 1; C
1~C
4The preferred molar ratio scope of alkanol and mineral acid is 1.5~5: 1, and more preferably molar ratio range is 1.8~3: 1; The preferred molar ratio scope of mineral acid and nitrite is 0.2~3: 1, and more preferably molar ratio range is 0.4~2: 1.
The technique scheme nitrite preferably in Sodium Nitrite or potassium nitrite at least one, more preferably from Sodium Nitrite; Mineral acid is preferably from sulfuric acid or nitric acid, more preferably from sulfuric acid; In the rotating bed super gravity field device, reaction conditions is preferably: temperature of reaction is 10~100 ℃, and reaction pressure is-0.05~1.0MPa, and be 0.01~30 second duration of contact.More preferably reaction conditions is: temperature of reaction is 10~60 ℃, and reaction pressure is-0.05~0.8MPa, and be 0.01~20 second duration of contact.
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 all because of gravity 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.
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 the contact gear ratio surface-area, make 1~3 order of magnitude of raising in interphase mass transfer speed ratio tradition tower or reactor, microcosmic mixing, mass transfer and heat transfer process also are greatly strengthened.Make the production efficiency of unit equipment volume obtain the raising of 1~2 order of magnitude.
Research shows, nitrite, mineral acid and C
1~C
4It is that speed of reaction is higher that alkanol reaction generates one of reaction characteristics of alkyl nitrite, two are the typical thermopositive reaction of this reaction process.And well-known, nitrous acid ester itself is again heat-sensitive substance, in the situation that local temperature is too high, easily decomposes, and when serious, can blast, and therefore, how to control equably reaction process, and then avoids part to occur that focus etc. is key problem in technology.Technical solution of the present invention is fully being studied nitrite, mineral acid and C
1~C
4On the basis of the characteristics of alkanol reaction, propose to adopt the rotating bed super gravity field device as reactor, take full advantage of the significant advantage that can how much orders of magnitude significantly improves rate of mass transfer and rate of heat transfer of rotating bed super gravity field device, and then effectively promote main reaction, the generation of side reaction of drawing up, thus the selectivity of nitrous acid ester greatly improved.In addition, consider raw material nitrite and product inorganic acid salt solubleness in the reaction system, in the present invention, adopt water as thinner, guarantee that raw material mixes on the one hand, the salt of simultaneously avoiding reaction to generate is separated out the obstruction reactive system with crystal, guarantees that reaction process is steadily stable.
Adopt technical scheme of the present invention, with Sodium Nitrite, sulfuric acid and C
1~C
4Alkanol is raw material, and water is thinner, usings the rotating bed super gravity field device as reactor, in the mol ratio of water and Sodium Nitrite, is 1~20: 1, C
1~C
4The mol ratio of alkanol and sulfuric acid is 1.5~5: 1, the mol ratio 0.2~3: 1 of sulfuric acid and Sodium Nitrite, temperature of reaction is 0~120 ℃, reaction pressure is-0.09~1.5MPa, under the condition that be 0.01~50 second duration of contact, raw material is contact reacts in the 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 99.8%, has obtained technique effect preferably.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 1: 1, the aqueous solution by Sodium Nitrite, methyl alcohol and sulfuric acid also flow to into the 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), the mol ratio of methyl alcohol and sulfuric acid is 1.5: 1, the mol ratio of sulfuric acid and Sodium Nitrite 0.9: 1, in temperature of reaction, it is 10 ℃, reaction pressure is-0.08MPa, be 0.01 second duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 500rpm condition, raw material is contact reacts in the rotating bed super gravity field device, its result is: the selectivity of methyl nitrite is 100%.
[embodiment 2]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 2: 1, by the aqueous solution of Sodium Nitrite, methyl alcohol and sulfuric acid and flow to into the rotating bed super gravity field reactor, the mol ratio of methyl alcohol and sulfuric acid is 2: 1, the mol ratio of sulfuric acid and Sodium Nitrite 0.3: 1, in temperature of reaction, it is 30 ℃, reaction pressure is-0.05MPa, be 0.05 second duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 800rpm condition, and raw material is contact reacts in the rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.98%.
[embodiment 3]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 18: 1, the aqueous solution by Sodium Nitrite, methyl alcohol and sulfuric acid also flow to into the rotating bed super gravity field reactor, the mol ratio of methyl alcohol and sulfuric acid is 3: 1, the mol ratio of sulfuric acid and Sodium Nitrite 0.5: 1, in temperature of reaction, it is 40 ℃, reaction pressure is-0.01MPa, be 0.1 second duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 1000rpm condition, raw material is contact reacts in the rotating bed super gravity field device, its result is: the selectivity of methyl nitrite is 99.99%.
[embodiment 4]
Potassium nitrite is dissolved in water, wherein, the mol ratio of water and potassium nitrite is 15: 1, by the aqueous solution of potassium nitrite, ethanol and sulfuric acid and flow to into the rotating bed super gravity field reactor, the mol ratio of ethanol and sulfuric acid is 5: 1, the mol ratio of sulfuric acid and potassium nitrite 0.6: 1, in temperature of reaction, it is 80 ℃, reaction pressure is 0.2MPa, be 0.3 second duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 1500rpm condition, and raw material is contact reacts in the rotating bed super gravity field device, and its result is: the selectivity of ethyl nitrite is 99.99%.
[embodiment 5]
Potassium nitrite is dissolved in water, wherein, the mol ratio of water and potassium nitrite is 10: 1, by the aqueous solution of potassium nitrite, propyl alcohol and sulfuric acid and flow to into the rotating bed super gravity field reactor, the mol ratio of propyl alcohol and sulfuric acid is 3: 1, the mol ratio of sulfuric acid and potassium nitrite 0.8: 1, in temperature of reaction, it is 110 ℃, reaction pressure is 0.5MPa, be 30 seconds duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 3500rpm condition, and raw material is contact reacts in the rotating bed super gravity field device, and its result is: the selectivity of propyl nitrite is 99.69%.
[embodiment 6]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 10: 1, by the aqueous solution of Sodium Nitrite, butanols and nitric acid and flow to into the rotating bed super gravity field reactor, the mol ratio of butanols and nitric acid is 2: 1, the mol ratio of nitric acid and Sodium Nitrite 2: 1, in temperature of reaction, it is 300 ℃, reaction pressure is 1.2MPa, be 10 seconds duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 5000rpm condition, and raw material is contact reacts in the rotating bed super gravity field device, and its result is: the selectivity of butyl nitrite is 99.89%.
[embodiment 7]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 2: 1, by the aqueous solution of Sodium Nitrite, methyl alcohol and sulfuric acid and flow to into the rotating bed super gravity field reactor, the mol ratio of methyl alcohol and sulfuric acid is 2: 1, the mol ratio of sulfuric acid and Sodium Nitrite 2: 1, in temperature of reaction, it is 50 ℃, reaction pressure is 0.2MPa, be 0.3 second duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 2000rpm condition, and raw material is contact reacts in the rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 99.99%.
[embodiment 8]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 4: 1, by the aqueous solution of Sodium Nitrite, methyl alcohol and sulfuric acid and flow to into the rotating bed super gravity field reactor, the mol ratio of methyl alcohol and sulfuric acid is 3: 1, the mol ratio of sulfuric acid and Sodium Nitrite 3: 1, in temperature of reaction, it is 60 ℃, reaction pressure is 0.02MPa, be 1 second duration of contact, the rotating speed of the rotor of rotating bed super gravity field device is under the 1000rpm condition, and raw material is contact reacts in the rotating bed super gravity field device, and its result is: the selectivity of methyl nitrite is 100%.
[comparative example 1]
Identical condition and the reaction raw materials according to embodiment 8, just adopt fixed-bed reactor, and its result is: the selectivity of methyl nitrite is 90.5%.
Claims (5)
1. produce C for one kind
1~C
4The method of alkyl nitriteester, with nitrite, mineral acid and C
1~C
4Alkanol is raw material, and water is thinner, usings the rotating bed super gravity field device as reactor, in temperature of reaction, be 10~100 ℃, reaction pressure is-0.05~1.0MPa, under the condition that be 0.01~30 second duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generates and contains C
1~C
4The effluent of alkyl nitriteester; Wherein, the mol ratio of described water and nitrite is 1~20: the mol ratio of 1, C1~C4 alkanol and mineral acid is 1.5~5: 1, the mol ratio 0.2~3: 1 of mineral acid and nitrite; Nitrite is selected from least one in Sodium Nitrite or potassium nitrite, and mineral acid is selected from sulfuric acid or nitric acid; C
1~C
4Alkanol is selected from methyl alcohol, ethanol or n-propyl alcohol; The rotating speed of the rotor of described rotating bed super gravity field device is 100~5000rpm.
2. produce according to claim 1 C
1~C
4The method of alkyl nitriteester, the mol ratio that it is characterized in that water and nitrite is 1.2~10: 1, C
1~C
4The mol ratio of alkanol and mineral acid is 1.8~3: 1, the mol ratio 0.4~2: 1 of mineral acid and nitrite.
3. produce according to claim 1 C
1~C
4The method of alkyl nitriteester, is characterized in that nitrite is selected from Sodium Nitrite, and mineral acid is selected from sulfuric acid; In the rotating bed super gravity field device, temperature of reaction is 10~60 ℃, and reaction pressure is-0.05~0.8MPa, and be 0.01~20 second duration of contact.
4. produce according to claim 1 C
1~C
4The method of alkyl nitriteester, the rotating speed that it is characterized in that the rotor of described rotating bed super gravity field device is 300~3000rpm.
5. produce according to claim 1 C
1~C
4The method of alkyl nitriteester is characterized in that: C
1~C
4Alkanol is selected from methyl alcohol or ethanol.
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CN103801242B (en) * | 2012-11-03 | 2015-12-02 | 中国石油化工股份有限公司 | Reactor and the alkylation reaction method utilizing this reactor |
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 |
CN105237402B (en) * | 2015-09-28 | 2017-11-14 | 山东朗恒化学有限公司 | A kind of continuous method and device for preparing nitrous acid ester |
Citations (5)
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---|---|---|---|---|
EP0310191A2 (en) * | 1987-09-29 | 1989-04-05 | Union Carbide Corporation | Process and reaction vessel for production of alkyl nitrite |
US20030149292A1 (en) * | 2000-04-03 | 2003-08-07 | Philippe Karrer | Method for preparing alkyl nitrites |
CN2581060Y (en) * | 2002-05-31 | 2003-10-22 | 湘潭大学 | Rotary bed ultragravity multi-phase reactor |
CN101104595A (en) * | 2007-04-26 | 2008-01-16 | 宁波万华聚氨酯有限公司 | Process for preparing isocyanate |
CN101125263A (en) * | 2007-06-11 | 2008-02-20 | 刘辉 | Vertical rotating bed super gravity field equipment |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4240311A1 (en) * | 1992-12-01 | 1994-06-09 | Bayer Ag | Process for the continuous production of alkyl nitrites |
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EP0310191A2 (en) * | 1987-09-29 | 1989-04-05 | Union Carbide Corporation | Process and reaction vessel for production of alkyl nitrite |
US20030149292A1 (en) * | 2000-04-03 | 2003-08-07 | Philippe Karrer | Method for preparing alkyl nitrites |
CN2581060Y (en) * | 2002-05-31 | 2003-10-22 | 湘潭大学 | Rotary bed ultragravity multi-phase reactor |
CN101104595A (en) * | 2007-04-26 | 2008-01-16 | 宁波万华聚氨酯有限公司 | Process for preparing isocyanate |
CN101125263A (en) * | 2007-06-11 | 2008-02-20 | 刘辉 | Vertical rotating bed super gravity field equipment |
Non-Patent Citations (1)
Title |
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