CN102275882B - Preparation method of NO needed for oxalate production - Google Patents
Preparation method of NO needed for oxalate production Download PDFInfo
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- CN102275882B CN102275882B CN2010102000135A CN201010200013A CN102275882B CN 102275882 B CN102275882 B CN 102275882B CN 2010102000135 A CN2010102000135 A CN 2010102000135A CN 201010200013 A CN201010200013 A CN 201010200013A CN 102275882 B CN102275882 B CN 102275882B
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Abstract
The invention relates to a preparation method of NO needed for oxalate production, which mainly solves the technical problems that in the prior art, the conversion rate of raw materials is low and the selectivity of target products is low. In a technical scheme adopted in the invention, byusing nitrite and inorganic acid as raw materials, water as a diluting agent, and a super-gravity field device of a rotating bed as a reactor, the raw materials are subjected to contact reaction in the super-gravity field device of the rotating bed under the conditions of reaction temperature of 0-120 DEG C, reaction pressure of minus 0.09-1.5Mpa and the contact time of 0.01-50 seconds to generate effluent containing NO. By means of the technical scheme, the problems are better solved. The preparation method can be applied to the industrial production of NO needed for the oxalate production.
Description
Technical field
The present invention relates to a kind of preparation method who produces the required NO of barkite, particularly about the preparation method of the required NO of CO coupling producing oxalic ester.
Background technology
Barkite is important Organic Chemicals, is used in a large number fine chemistry industry and 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 get oxalic acid, and normal pressure ammonia solution can get 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 pharmaceutically as the chest acyl alkali of hormone.In addition, the barkite low-voltage hydrogenation can prepare 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, and import volume was nearly 4,800,000 tons in 2007 years.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and the production technique cost is high, and energy consumption is large, 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 Oxidation of Carbon Monoxide 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 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)
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 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 gases; need to replenish 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, this production method directly is used as with the oxynitride that the air ammonia oxidation generates the NO gas that synthesis of oxalate is used, perhaps directly be used as with the oxynitride in nitric acid industry tail gas 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 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 its oxygen concentration 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 flow process on the one hand is complicated, and operation energy consumption is high, 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 EP0023745 A3 patent that Britain Imperial Chemical Industries (ICI) propose is mentioned rotating bed and be 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 the oil-field flooding deoxidation; CN1116146A discloses a kind of method for preparing 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, research for application and development is still constantly being carried out, new Application Areas is also in continuous developing, also is not applied to produce for now the preparation method's of the required NO of barkite report about rotating bed.Especially do not produce about nitrite and inorganic acid reaction the report that NO adopts high-gravity technology.
Summary of the invention
Technical problem to be solved by this invention is the technical problem that the feed stock conversion that exists in previous literature is low, the NO selectivity is low, and the preparation method of a kind of new required NO of production barkite is provided.The method has advantages of that feed stock conversion is low and the NO 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 preparation method who produces the required NO of barkite, take nitrite and mineral acid as raw material, water is thinner, as reactor, is 0～120 ℃ in temperature of reaction with the rotating bed super gravity field device, reaction pressure is-0.09～1.5MPa, be that under the condition of 0.01～50 second, raw material is contact reacts in the rotating bed super gravity field device duration of contact, generates the effluent that contains NO.
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; The preferred molar ratio scope of mineral acid and nitrite is 0.2～5: 1, and more preferably molar ratio range is 0.4～3: 1.
The technique scheme nitrite is preferably at least a in Sodium Nitrite or potassium nitrite, 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 preferred speed range is 300～3000rpm.
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.
Studies show that, it is that speed of reaction is very fast that nitrite and inorganic acid reaction generate one of reaction characteristics of NO, and reaction process is subjected to diffusion control, two are the typical thermopositive reaction of this reaction process, its three, the purity of reaction product NO is higher.Therefore, reinforcing mass transfer process how, and to remove fast and effectively heat be the key problem in technology that efficiently prepares NO.Technical solution of the present invention is on the basis of the characteristics of fully studying nitrite and inorganic acid 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, thereby selectivity and the reaction efficiency of purpose product have greatly been improved.In addition, consider raw material nitrite and product inorganic acid salt solubleness in the reaction system, adopt water as thinner in the present invention, guarantee that raw material mixes on the one hand, 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, take Sodium Nitrite and sulfuric acid as raw material, water is thinner, with the rotating bed super gravity field device as reactor, mol ratio at water and Sodium Nitrite is 1～20: 1, the mol ratio 0.2～5: 1 of sulfuric acid and Sodium Nitrite, temperature of reaction is 0～120 ℃, reaction pressure is-0.09～1.5MPa, be under the condition of 0.01～50 second duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generation contains the effluent of NO, wherein feed stock conversion can reach 100%, the selectivity of NO can be greater than 99.8%, obtained technique effect preferably.
The invention will be further elaborated below by embodiment, 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, with the aqueous solution and the sulfuric acid of Sodium Nitrite and 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 sulfuric acid and Sodium Nitrite 0.9: 1, it is 10 ℃ in temperature of reaction, 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 transformation efficiency of Sodium Nitrite is 100%, the selectivity of NO is 100%.
[embodiment 2]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 2: 1, with the aqueous solution and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of sulfuric acid and Sodium Nitrite 0.5: 1, it is 30 ℃ in temperature of reaction, 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, raw material is contact reacts in the rotating bed super gravity field device, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 100%, NO is 99.98%.
[embodiment 3]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 18: 1, with the aqueous solution and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of sulfuric acid and Sodium Nitrite 0.55: 1, it is 40 ℃ in temperature of reaction, 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, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 100%, NO is 99.99%.
[embodiment 4]
Potassium nitrite is dissolved in water, wherein, the mol ratio of water and potassium nitrite is 15: 1, with the aqueous solution and the sulfuric acid of potassium nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of sulfuric acid and potassium nitrite 0.6: 1, it is 80 ℃ in temperature of reaction, 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, raw material is contact reacts in the rotating bed super gravity field device, and its result is: the transformation efficiency of potassium nitrite is that the selectivity of 100%, NO is 99.99%.
[embodiment 5]
Potassium nitrite is dissolved in water, wherein, the mol ratio of water and potassium nitrite is 10: 1, with the aqueous solution sulfuric acid of potassium nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of sulfuric acid and potassium nitrite 0.8: 1, it is 110 ℃ in temperature of reaction, 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, raw material is contact reacts in the rotating bed super gravity field device, and its result is: the transformation efficiency of potassium nitrite is that the selectivity of 100%, NO is 99.69%.
[embodiment 6]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 10: 1, with the aqueous solution and the nitric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of nitric acid and Sodium Nitrite 2.1: 1, it is 300 ℃ in temperature of reaction, 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, raw material is contact reacts in the rotating bed super gravity field device, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 100%, NO is 99.89%.
[embodiment 7]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 2: 1, with the aqueous solution and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of sulfuric acid and Sodium Nitrite 2: 1, it is 50 ℃ in temperature of reaction, 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, raw material is contact reacts in the rotating bed super gravity field device, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 100%, NO is 99.99%.
[embodiment 8]
Sodium Nitrite is dissolved in water, wherein, the mol ratio of water and Sodium Nitrite is 4: 1, with the aqueous solution and the sulfuric acid of Sodium Nitrite and flow to into the rotating bed super gravity field reactor, the mol ratio of sulfuric acid and Sodium Nitrite 3: 1, it is 60 ℃ in temperature of reaction, 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, raw material is contact reacts in the rotating bed super gravity field device, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 100%, NO is 100%.
[comparative example 1]
According to the identical condition of embodiment 7, reaction times and reaction raw materials just adopt stirred-tank reactor, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 70%, NO is 97.5%.
[comparative example 2]
According to the identical condition of embodiment 8, reaction times and reaction raw materials just adopt stirred-tank reactor, and its result is: the transformation efficiency of Sodium Nitrite is that the selectivity of 80%, NO is 95.5%.
Claims (6)
1. preparation method who produces the required NO of barkite, take nitrite and mineral acid as raw material, water is thinner, as reactor, be 0～120 ℃ in temperature of reaction with the rotating bed super gravity field device, reaction pressure is-0.09～1.5MPa, be under the condition of 0.01～50 second duration of contact, raw material is contact reacts in the rotating bed super gravity field device, generates the effluent that contains NO, and the rotating speed of the rotor of described rotating bed super gravity field device is 100～5000rpm.
2. produce according to claim 1 the preparation method of the required NO of barkite, the mol ratio that it is characterized in that water and nitrite is 1～20: 1, the mol ratio 0.2～5: 1 of mineral acid and nitrite.
3. produce according to claim 2 the preparation method of the required NO of barkite, the mol ratio that it is characterized in that water and nitrite is 1.2～10: 1, the mol ratio 0.4～3: 1 of mineral acid and nitrite.
4. produce according to claim 1 the preparation method of the required NO of barkite, it is characterized in that nitrite is selected from Sodium Nitrite or potassium nitrite at least a, mineral acid is selected from sulfuric acid or nitric acid; 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.
5. produce according to claim 4 the preparation method of the required NO of barkite, it is characterized in that nitrite is selected from Sodium Nitrite, 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.
6. produce according to claim 1 the preparation method of the required NO of barkite, the rotating speed that it is characterized in that the rotor of described rotating bed super gravity field device is 300～3000rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895766A (en) * | 2005-07-14 | 2007-01-17 | 中国石油化工股份有限公司 | Catalytic selective hydrogenation |
| CN101428773A (en) * | 2008-12-11 | 2009-05-13 | 大连光明特种气体有限公司 | Purifying method for nitric oxide gas with 3N purity |
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| JPH0761846B2 (en) * | 1989-04-21 | 1995-07-05 | 宇部興産株式会社 | High-concentration NO ▲ lower x ▼ Gas manufacturing method and apparatus |
| US20040028596A1 (en) * | 2002-08-12 | 2004-02-12 | Bela Kleiner | Nitrogen dioxide, nitrogen oxide and nitric acid manufacture: Kleiner method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895766A (en) * | 2005-07-14 | 2007-01-17 | 中国石油化工股份有限公司 | Catalytic selective hydrogenation |
| CN101428773A (en) * | 2008-12-11 | 2009-05-13 | 大连光明特种气体有限公司 | Purifying method for nitric oxide gas with 3N purity |
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