CN102276472A - Method for producing C1-C4 alkyl nitrite - Google Patents
Method for producing C1-C4 alkyl nitrite Download PDFInfo
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- CN102276472A CN102276472A CN2010101999414A CN201010199941A CN102276472A CN 102276472 A CN102276472 A CN 102276472A CN 2010101999414 A CN2010101999414 A CN 2010101999414A CN 201010199941 A CN201010199941 A CN 201010199941A CN 102276472 A CN102276472 A CN 102276472A
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- acid ester
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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 nitrous acid ester is particularly about the required C of CO coupling producing oxalic ester
1～C
4The replenishing 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 be produced crucial 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 import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid with alcohol esterification to take place and produces, production technique cost height, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking an operational path that cost is low, environment is good always.The sixties in last century, the D.F.Fenton of U.S. Associated Oil Company finds, carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative coupling method synthesis of oxalate and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer easily runs off in the reaction process.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
The reaction process of synthesis of oxalate is as follows:
Linked reaction 2CO+2RONO → 2NO+ (COOR)
2(1)
Regenerative response 2ROH+0.5O
2+ 2NO → 2RONO+H
2O (2)
By said process as can be known; theoretically; this reaction process is not consume NO, and still, 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 by product nitric acid to generate, this must consume more NO gases; need in system, to replenish oxynitride, 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, this production method directly is used as the NO gas that synthesis of oxalate is used with the oxynitride that the air ammonia oxidation generates, perhaps directly be used as the NO gas that synthesis of oxalate is used with the oxynitride in the nitric acid industry tail gas, and adopt alcohols to absorb nitrous acid ester, and the method that adopts compression and condensation to combine fully reclaims alcohols and nitrous acid ester in the discharging tail gas.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%; Used pressure is 0.1～10MPa, and used condensing temperature is at-20 ℃～100 ℃.Shortcomings such as the production method of this oxynitride is the flow process complexity on the one hand, and the operation energy consumption height simultaneously, exists selectivity low in the oxynitride process that the production synthesis of oxalate is used, and side reaction is many, and raw material availability is low.
The EP0023745A3 patent that Britain Imperial Chemical Industries (ICI) propose is mentioned rotating bed and be can be used for processes such as absorption, parsing, distillation, but does not disclose the utilisation technology of industrially scalable.CN1064338A discloses the method for utilizing rotating bed to carry out the oil-field flooding deoxidation; CN1116146A discloses a kind of method of producing ultrafine particle under super gravity field.
The super gravity field technology is the new technology that early eighties just occurs, and its internal mechanism is also continuing exploration, and research for application and development is still constantly being carried out, and new Application Areas also is applied to C about rotating bed for now also in continuous developing
1～C
4The report that the alkyl nitrous acid ester is produced.Especially do not produce C about nitrite, mineral acid and C1～C4 alkyl alcohol reaction
1～C
4The alkyl nitrous acid ester adopts the report of high-gravity technology.
Summary of the invention
Technical problem to be solved by this invention is the C that in the past exists in the document
1～C
4The technical problem that alkyl nitrous acid ester selectivity is low provides a kind of new production C
1～C
4The method of alkyl nitrous acid ester.This method has C
1～C
4The advantage that alkyl nitrous acid ester selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production C
1～C
4The method of alkyl nitrous acid ester is with nitrite, mineral acid and C
1～C
4Alkanol is a raw material, and water is thinner, with the rotating bed super gravity field device as reactor, in temperature of reaction is 0～120 ℃, and reaction pressure is-0.09～1.5MPa, and be under 0.01～50 second the condition duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generates to contain C
1～C
4The effluent of alkyl nitrous acid ester.
The preferred molar ratio scope of water and nitrite is 1～20: 1 in the technique scheme, 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.
Nitrite is preferably at least a in Sodium Nitrite or potassium nitrite in the technique scheme, more preferably from Sodium Nitrite; Mineral acid is preferably from sulfuric acid or nitric acid, more preferably from sulfuric acid; Reaction conditions is preferably in the rotating bed super gravity field device: 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.
The rotating speed of the rotor of rotating bed super gravity field device is 100～5000rpm in the technique scheme, and preferred 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, all substances are all attracted by the earth because of gravity on the earth, super gravity field is the environment more much bigger than earth gravity intensity of field, and material suffered power under super gravity field is called hypergravity, utilizes hypergravity the principles of science and the practical technique that produces is called high-gravity technology.
Under the hypergravity environment bigger hundreds of times to thousand times than earth gravity field, great shear forces is torn into liquid liquid film, brin, the drop of micron to nano grade, produce phase interface huge, fast updating, greatly increased the contact gear ratio surface-area, make 1～3 order of magnitude of raising in interphase mass transfer speed ratio tradition tower or the reactor, microcosmic mixing, mass transfer and heat transfer process are also greatly strengthened.Make the production efficiency of unit equipment volume obtain the raising of 1～2 order of magnitude.
Studies show that 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 a heat-sensitive substance, decomposes easily under the too high situation of local temperature, can blast when serious, therefore, how to control reaction process equably, and then to avoid the part focus etc. to occur be 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, make full use 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, adopt water among the present invention, guarantee that raw material mixes on the one hand as thinner, the salt of avoiding simultaneously reacting generation 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 a raw material, and water is thinner, as reactor, is 1～20: 1 in the mol ratio of water and Sodium Nitrite with the rotating bed super gravity field device, C
1～C
4Alkanol and vitriolic mol ratio are 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, be under 0.01～50 second the condition duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generates to contain C
1～C
4The effluent of alkyl nitrous acid ester, wherein C
1～C
4The selectivity of alkyl nitrous acid ester can obtain better technical effect greater than 99.8%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Sodium Nitrite is dissolved in the water, wherein, the mol ratio of water and Sodium Nitrite is 1: 1, the aqueous solution with 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 among the embodiment 1 among the patent CN1895766A identical (following identical), methyl alcohol and vitriolic mol ratio are 1.5: 1, the mol ratio of sulfuric acid and Sodium Nitrite 0.9: 1, in temperature of reaction 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, and its result is: the selectivity of methyl nitrite is 100%.
[embodiment 2]
Sodium Nitrite is dissolved in the water, wherein, the mol ratio of water and Sodium Nitrite is 2: 1, with the aqueous solution, methyl alcohol and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, methyl alcohol and vitriolic mol ratio are 2: 1, the mol ratio of sulfuric acid and Sodium Nitrite 0.3: 1, in temperature of reaction 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 the water, wherein, the mol ratio of water and Sodium Nitrite is 18: 1, with the aqueous solution, methyl alcohol and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, methyl alcohol and vitriolic mol ratio are 3: 1, the mol ratio of sulfuric acid and Sodium Nitrite 0.5: 1, in temperature of reaction 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, 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 4]
Potassium nitrite is dissolved in the water, wherein, the mol ratio of water and potassium nitrite is 15: 1, with the aqueous solution, ethanol and the sulfuric acid of potassium nitrite and flow to into the rotating bed super gravity field reactor, ethanol and vitriolic mol ratio are 5: 1, the mol ratio of sulfuric acid and potassium nitrite 0.6: 1, in temperature of reaction 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 the water, wherein, the mol ratio of water and potassium nitrite is 10: 1, with the aqueous solution, propyl alcohol and the sulfuric acid of potassium nitrite and flow to into the rotating bed super gravity field reactor, propyl alcohol and vitriolic mol ratio are 3: 1, the mol ratio of sulfuric acid and potassium nitrite 0.8: 1, in temperature of reaction 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 the water, wherein, the mol ratio of water and Sodium Nitrite is 10: 1, with the aqueous solution, butanols and the nitric acid of Sodium Nitrite 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 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 the water, wherein, the mol ratio of water and Sodium Nitrite is 2: 1, with the aqueous solution, methyl alcohol and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, methyl alcohol and vitriolic mol ratio are 2: 1, the mol ratio of sulfuric acid and Sodium Nitrite 2: 1, in temperature of reaction 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 the water, wherein, the mol ratio of water and Sodium Nitrite is 4: 1, with the aqueous solution, methyl alcohol and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, methyl alcohol and vitriolic mol ratio are 3: 1, the mol ratio of sulfuric acid and Sodium Nitrite 3: 1, in temperature of reaction 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]
According to embodiment 8 identical condition and reaction raw materials, just adopt fixed-bed reactor, its result is: the selectivity of methyl nitrite is 90.5%.
Claims (9)
1. produce C for one kind
1～C
4The method of alkyl nitrous acid ester is with nitrite, mineral acid and C
1～C
4Alkanol is a raw material, and water is thinner, with the rotating bed super gravity field device as reactor, in temperature of reaction is 0～120 ℃, and reaction pressure is-0.09～1.5MPa, and be under 0.01～50 second the condition duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generates to contain C
1～C
4The effluent of alkyl nitrous acid ester.
2. according to the described production of claim 1 C
1～C
4The method of alkyl nitrous acid ester, the mol ratio that it is characterized in that water and nitrite is 1～20: 1, C
1～C
4The mol ratio of alkanol and mineral acid is 1.5～5: 1, the mol ratio 0.2～3: 1 of mineral acid and nitrite.
3. according to the described production of claim 2 C
1～C
4The method of alkyl nitrous acid ester, 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.
4. according to the described production of claim 1 C
1～C
4The method of alkyl nitrous acid ester, it is at least a to it is characterized in that nitrite is selected from Sodium Nitrite or the potassium nitrite, and mineral acid is selected from sulfuric acid or nitric acid; Temperature of reaction is 10～100 ℃ in the rotating bed super gravity field device, and reaction pressure is-0.05～1.0MPa, and be 0.01～30 second duration of contact.
5. according to the described production of claim 4 C
1～C
4The method of alkyl nitrous acid ester is characterized in that nitrite is selected from Sodium Nitrite, and mineral acid is selected from sulfuric acid; Temperature of reaction is 10～60 ℃ in the rotating bed super gravity field device, and reaction pressure is-0.05～0.8MPa, and be 0.01～20 second duration of contact.
6. according to the described production of claim 1 C
1～C
4The method of alkyl nitrous acid ester, the rotating speed that it is characterized in that the rotor of described rotating bed super gravity field device is 100～5000rpm.
7. according to the described production of claim 6 C
1～C
4The method of alkyl nitrous acid ester, the rotating speed that it is characterized in that the rotor of described rotating bed super gravity field device is 300～3000rpm.
8. according to the described production 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. described according to Claim 8 production C
1～C
4The method of alkyl nitrous acid ester is characterized in that: C
1～C
4Alkanol is selected from methyl alcohol or ethanol.
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| CN2010101999414A CN102276472B (en) | 2010-06-11 | 2010-06-11 | Method for producing C1-C4 alkyl nitrite |
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|---|---|---|---|
| CN2010101999414A CN102276472B (en) | 2010-06-11 | 2010-06-11 | Method for producing C1-C4 alkyl nitrite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801242A (en) * | 2012-11-03 | 2014-05-21 | 中国石油化工股份有限公司 | Reactor and alkylation reaction method using same |
| 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 |
| CN105237402A (en) * | 2015-09-28 | 2016-01-13 | 山东朗恒化学有限公司 | Method and device capable of continuously preparing nitrous acid ester |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801242A (en) * | 2012-11-03 | 2014-05-21 | 中国石油化工股份有限公司 | Reactor and alkylation reaction method using same |
| 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 |
| US9446996B2 (en) | 2012-11-03 | 2016-09-20 | China Petroleum & Chemical Corporation | Reactor and alkylation process using the reactor |
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| CN105237402A (en) * | 2015-09-28 | 2016-01-13 | 山东朗恒化学有限公司 | Method and device capable of continuously preparing nitrous acid ester |
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| CN102276472B (en) | 2013-12-04 |
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