CN201770631U - Super-gravity reactor - Google Patents
Super-gravity reactor Download PDFInfo
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- CN201770631U CN201770631U CN2010201603681U CN201020160368U CN201770631U CN 201770631 U CN201770631 U CN 201770631U CN 2010201603681 U CN2010201603681 U CN 2010201603681U CN 201020160368 U CN201020160368 U CN 201020160368U CN 201770631 U CN201770631 U CN 201770631U
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Abstract
The utility model relates to a super-gravity reactor, which mainly solves the technical problem of low selectivity of alkyl nitrite of objective products in the prior art. The technical scheme adopted by the super-gravity reactor includes that the super-gravity reactor comprises a reactor casing (1), a rotor (5), a gas partition plate (7), a liquid inlet (3) and a gas outlet (4), and is characterized in that an upper filler layer (6) and a lower filler layer (15) are arranged inside the super-gravity reactor, a first gas inlet (2) and a second gas inlet (16) are further arranged on the lower side of the lower filler layer (15), and a liquid distributor (8) is arranged inside a pipeline of the liquid inlet (3). Accordingly, the super-gravity reactor more effectively solves the problem and can be used for industrial production of C1-C4 alkyl nitrite production increasing.
Description
Technical field
The utility model relates to a kind of supergravity reactor, particularly produces C about CO coupling producing oxalic ester
1～C
4The supergravity reactor that the alkyl nitrous acid ester is required.
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 prepare crucial 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.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, 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 the key problem in technology of this system be to make the high efficiency reasonable use of NO, RONO, ROH highly selective in the two-step reaction process.
But 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 the rare nitric acid of by product to generate, this must consume more NO gases; increase energy consumption and cost, also can bring equipment corrosion etc. simultaneously.Although more about document how to produce the alkyl nitrous acid ester, the relevant selectivity that how effectively to improve alkyl nitrite prevents that better 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 loaded catalyst, coupling generates the oxalic acid diethyl ester crude product, reaction is self-enclosed working cycle, CO gas enters coupler reactor with ethyl nitrite from regeneration reactor through mixing preheating, reaction back gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, the non-condensable gas that contains 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, does not mention the selectivity of ethyl nitrite among the present invention.
Document CN 95116136.9 discloses the catalyzer of the synthetic usefulness of a kind of barkite, selects for use Zr to make auxiliary agent, develops novel Pd-Zr/Al with pickling process
2O
3Catalyzer.This catalyzer is to adopt fixed-bed reactor as carbon monoxide and the reaction of nitrous acid ester synthesis of oxalic ester by gaseous catalysis.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 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 for preparing 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 is also in continuous developing, for now also not about the rotary packed bed C that is applied to
1～C
4The report that the alkyl nitrous acid ester is produced.
Summary of the invention
Technical problem to be solved in the utility model 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 supergravity reactor.This reactor has production 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 adopted in the utility model is as follows: a kind of supergravity reactor, comprise reactor shell, rotor, gas barrier, liquid-inlet and pneumatic outlet, wherein, packing layer and following packing layer are set in the supergravity reactor, the downside of following packing layer also is provided with first gas feed and second gas feed, in the fluid inlet pipeline liquid distributor is set.
Last packing layer and following packing layer in the supergravity reactor in the technical program, supergravity reactor wherein are two-layer coaxial packing layer.The gas outlet of supergravity reactor is provided with mist eliminator.
Supergravity reactor of the present utility model since adopted relatively simple for structure, huge tower in the little rotary packed bed replacement traditional technology of volume.Make total system compact to design, easy and simple to handle, the operation and maintenance cost is low, and floor space is little, and turndown ratio is big.Can reduce processing cost significantly.The setting of two gas inletes in the rotary packed bed reactor simultaneously, and two-layer coaxial packing layer both can have been avoided the pre-mixing of oxynitride and oxygen and the N that causes
2O
4Generation, and then significantly improve the selectivity of alkyl nitrous acid ester, guaranteed enough residence time again simultaneously, guarantee to react thoroughly, improve conversion of raw material.
Description of drawings
Fig. 1 is the supergravity reactor result schematic diagram.
The 1-reactor shell 2-first gas feed 3-liquid-inlet 4-pneumatic outlet 5-rotor 6-goes up the packing layer 16-second gas feed 17-first gas feed pipeline 18-second gas feed pipeline under the packing layer 7-gas barrier 8-liquid distributor 9-mist eliminator 10-liquid air seal set 11-liquid exit 12-bearing 13-rotating shaft 14-magnet steel assembly 15-among the figure.
Embodiment
Below in conjunction with accompanying drawing the utility model supergravity reactor is elaborated.
Supergravity reactor of the present utility model, employing comprises reactor shell 1, rotor 5, gas barrier 7, liquid-inlet 3 and pneumatic outlet 4, packing layer 6 and following packing layer 15 wherein are set in the supergravity reactor, the downside of following packing layer 15 also is provided with first gas feed 2 and second gas feed 16, two gas inletes enter oxides of nitrogen gas raw material and oxygen respectively, in fluid inlet 3 pipelines liquid distributor 8 is set, fluid inlet 3 enters C1～C4 alkyl alcohol.Last packing layer 6 and following packing layer 15 in the supergravity reactor are two-layer coaxial packing layer, and pneumatic outlet 4 places of supergravity reactor are provided with mist eliminator 9.Rotation filler power motor preferably adopts frequency control motor.
During work gas, the oxygen of nitrogen-containing oxide are introduced in the reactor shell 1 from first gas inlet 2, second gas inlet 16 respectively, merge contact reacts with the descending liquid that comes to go up in the reactor shell 1 packing layer 6 premix in following packing layer 15, wherein the introducing of nitrogen-containing oxide G﹠O is to be realized by the negative pressure that system forms.C
1～C
4Alkyl alcohol is by fluid inlet 3 and enter liquid distributor 8 and upper strata filler 6, and gas, liquid further fully contact in the filler of upper strata, and the way of contact adopts adverse current, cross-flow all can.Nitrogenous compound in the gas and oxygen and C1～C4 alkyl alcohol is through after reacting, contain C1～C4 alkyl nitrous acid ester gas by after mist eliminator 9 foam removals, discharge by venting port 4, liquid is by 1 time packing layer of reactor shell, after the further hybrid reaction of gas, discharge by liquid exit 11 from first gas feed 2 and second gas feed 16.
The rotating speed of rotation filler is 100～10000rpm in the above-mentioned supergravity reactor, wherein rotate the selected main inlet amount decision of filler rotating speed by oxynitride, if the motor of rotation filler is a frequency control motor, then can be in above-mentioned rotating speed according to the inlet amount and the C of oxynitride
1～C
4Alkyl alcohol introducing amount is adjusted continuously.
Below by embodiment the utility model is further elaborated, but is not limited only to present embodiment.
[embodiment 1]
The gas volume of first gas of nitrogen-containing oxide raw material is 100m
3/ h, wherein, the concentration of NO is 10%v (all the other are nitrogen), the gas volume 2m of the second gas oxygen
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 2000rpm.Methanol solution enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, methanol solution mol ratio are 1: 30 in the gas, gas and liquid counter current contact in the packing layer 6 on supergravity reactor, reaction generates gaseous effluent I and the liquid efflunent II that contains methyl nitrite.The gaseous effluent I that contains methyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 20 ℃, and pressure is 1atm, and its result is, the selectivity of methyl nitrite is 99.81%, and the transformation efficiency of oxygen is 100%.
[embodiment 2]
The gas volume of first gas of nitrogen-containing oxide raw material is 100m
3/ h, wherein, the concentration of NO is 21%v (all the other are nitrogen), the gas volume 3.8m of the second gas oxygen
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 4000rpm.Methanol solution enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, methanol solution mol ratio are 1: 15 in the gas, gas and liquid counter current contact in the packing layer 6 on supergravity reactor, reaction generates gaseous effluent I and the liquid efflunent II that contains methyl nitrite.The gaseous effluent I that contains methyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 30 ℃, and pressure is 1atm, and its result is, the selectivity of methyl nitrite is 99.75%, and the transformation efficiency of oxygen is 100%.
[embodiment 3]
The gas volume of first gas of nitrogen-containing oxide raw material is 100m
3/ h, wherein, the concentration of NO is 15%v (all the other are nitrogen), the gas volume 2.4m of the second gas oxygen
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 6000rpm.Methanol solution enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, methanol solution mol ratio are 1: 50 in the gas, gas and liquid counter current contact in the packing layer 6 on supergravity reactor, reaction generates gaseous effluent I and the liquid efflunent II that contains methyl nitrite.The gaseous effluent I that contains methyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 40 ℃, and pressure is 2atm, and its result is, the selectivity of methyl nitrite is 99.71%, and the transformation efficiency of oxygen is 100%.
[embodiment 4]
The gas volume of first gas of nitrogen-containing oxide raw material is 100m
3/ h, wherein, the concentration of NO is 36%v (all the other are nitrogen), the gas volume 3.7m of the second gas oxygen
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 2500rpm.Ethanolic soln enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, ethanol liquid mol ratio are 1: 50 in the gas, gas and liquid counter current contact in the packing layer 6 on supergravity reactor, reaction generates gaseous effluent I and the liquid efflunent II that contains ethyl nitrite.The gaseous effluent I that contains ethyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 40 ℃, and pressure is 2atm, and its result is, the selectivity of ethyl nitrite is 99.70%, and the transformation efficiency of oxygen is 100%.
[embodiment 5]
The gas volume of first gas of nitrogen-containing oxide raw material is 1000m
3/ h, wherein, the concentration of NO is 8%v (all the other are nitrogen), the gas volume 18m of the second gas oxygen
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 2500rpm.Propanol solution enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, propyl alcohol liquid mol ratio are 1: 10 in the gas, gas and liquid counter current contact in the packing layer 6 on supergravity reactor, reaction generates gaseous effluent I and the liquid efflunent II that contains propyl nitrite.The gaseous effluent I that contains propyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 50 ℃, and pressure is 0.2atm, and its result is, the selectivity of propyl nitrite is 99.68%, and the transformation efficiency of oxygen is 100%.
[embodiment 6]
The gas volume of first gas of nitrogen-containing oxide raw material is 100m
3/ h, wherein, the concentration of NO is 40%v (all the other are nitrogen), the gas volume 6m of the second gas oxygen
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 3000rpm.Methanol solution enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, methanol solution mol ratio are 1: 2 in the gas, gas also flows in the packing layer 6 on supergravity reactor with liquid and contacts, and reaction generates gaseous effluent I and the liquid efflunent II that contains methyl nitrite.The gaseous effluent I that contains methyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 30 ℃, and pressure is 1atm, and its result is, the selectivity of methyl nitrite is 99.71%, and the transformation efficiency of oxygen is 100%.
[embodiment 7]
The gas volume of first gas of nitrogen-containing oxide raw material is 100m
3/ h, wherein, the concentration of NO is 40%v, NO
2Concentration be 3%v, (all the other are nitrogen), the gas volume 18m of second gas air
3/ h, two kinds of gases enter in the supergravity reactor from first gas inlet 2 and second gas inlet 16 respectively, under differential pressure action, diffuse into lower floor's filler 15, and rotation filler rotating speed transfers to 5000rpm.Methanol solution enters the liquid distributor 8 of supergravity reactor and sprays to the filler inboard by liquid-inlet 3, oxynitride, methanol solution mol ratio are 1: 12 in the gas, gas and liquid on supergravity reactor in the packing layer 6 cross-flow contact, reaction generates gaseous effluent I and the liquid efflunent II that contains methyl nitrite.The gaseous effluent I that contains methyl nitrite sends into follow-up system by pneumatic outlet 4 after by the mist eliminator of rotary packed bed reactor 1, liquid efflunent II enters 1 time packing layer 15 of rotary packed bed reactor, after the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged by liquid exit 11.Temperature of reaction is 40 ℃, and pressure is 1atm, and its result is, the selectivity of methyl nitrite is 99.73%, and the transformation efficiency of oxygen is 100%.
Claims (3)
1. supergravity reactor, comprise reactor shell (1), rotor (5), gas barrier (7), liquid-inlet (3) and pneumatic outlet (4), it is characterized in that being provided with in the supergravity reactor packing layer (6) and following packing layer (15), the downside of following packing layer (15) also is provided with first gas feed (2) and second gas feed (16), in fluid inlet (3) pipeline liquid distributor (8) is set.
2. according to the described supergravity reactor of claim 1, it is characterized in that last packing layer (6) and the following packing layer (15) in the supergravity reactor is two-layer coaxial packing layer.
3. according to the described supergravity reactor of claim 1, it is characterized in that the pneumatic outlet (4) of supergravity reactor locates to be provided with mist eliminator (9).
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010201603681U CN201770631U (en) | 2010-04-15 | 2010-04-15 | Super-gravity reactor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010201603681U CN201770631U (en) | 2010-04-15 | 2010-04-15 | Super-gravity reactor |
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| CN201770631U true CN201770631U (en) | 2011-03-23 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110257425A1 (en) * | 2010-04-15 | 2011-10-20 | Juntao Liu | Process for Producing Cl-C4 Alkyl Nitrite |
| WO2011153825A1 (en) * | 2010-06-11 | 2011-12-15 | 中国石油化工股份有限公司 | Process for preparing oxalate by carbon monoxide gas-phase method |
| CN104387258A (en) * | 2014-11-07 | 2015-03-04 | 中国天辰工程有限公司 | Chloroacetic acid production method and chlorination reactor |
| CN107303459A (en) * | 2016-04-25 | 2017-10-31 | 云南民族大学 | The innoxious removing low concentration of NO of high-gravity technologyxDevice |
| CN114699939A (en) * | 2022-04-11 | 2022-07-05 | 北京化工大学 | Hypergravity gas mixing device for cutting bubbles step by step and application thereof |
-
2010
- 2010-04-15 CN CN2010201603681U patent/CN201770631U/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110257425A1 (en) * | 2010-04-15 | 2011-10-20 | Juntao Liu | Process for Producing Cl-C4 Alkyl Nitrite |
| US8722918B2 (en) * | 2010-04-15 | 2014-05-13 | China Petroleum & Chemical Corporation | Process for producing Cl-C4 alkyl nitrite |
| WO2011153825A1 (en) * | 2010-06-11 | 2011-12-15 | 中国石油化工股份有限公司 | Process for preparing oxalate by carbon monoxide gas-phase method |
| CN104387258A (en) * | 2014-11-07 | 2015-03-04 | 中国天辰工程有限公司 | Chloroacetic acid production method and chlorination reactor |
| CN104387258B (en) * | 2014-11-07 | 2016-03-09 | 中国天辰工程有限公司 | A kind of production of chloroacetic acid method and chlorination reactor |
| CN107303459A (en) * | 2016-04-25 | 2017-10-31 | 云南民族大学 | The innoxious removing low concentration of NO of high-gravity technologyxDevice |
| CN114699939A (en) * | 2022-04-11 | 2022-07-05 | 北京化工大学 | Hypergravity gas mixing device for cutting bubbles step by step and application thereof |
| CN114699939B (en) * | 2022-04-11 | 2023-08-29 | 北京化工大学 | Supergravity gas mixing device for gradually cutting bubbles and application thereof |
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Granted publication date: 20110323 |