CN102274671A - Method for removing nitrogen oxides from tail gas discharged in preparation of oxalate from CO - Google Patents
Method for removing nitrogen oxides from tail gas discharged in preparation of oxalate from CO Download PDFInfo
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- CN102274671A CN102274671A CN2010102000116A CN201010200011A CN102274671A CN 102274671 A CN102274671 A CN 102274671A CN 2010102000116 A CN2010102000116 A CN 2010102000116A CN 201010200011 A CN201010200011 A CN 201010200011A CN 102274671 A CN102274671 A CN 102274671A
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- oxalate
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Abstract
The invention relates to a method for removing nitrogen oxides from a tail gas discharged in preparation of oxalate from CO, which mainly solves a technical problem of low nitrogen oxide or nitrous acid ester removal rate in previous technologies. According to the invention, a discharged tail gas flow containing the nitrogen oxides is contacted with an adsorbent by going through an adsorbent bed in conditions that the temperature is -20-100DEG C, the pressure is 0.1-3.0MPa, and the liquid hourly space velocity is 100-5000h<-1>, and an effluent with no nitrogen oxides is obtained after adsorption, wherein the adsorbent is selected from at least one of ZSM molecular sieve, 5A molecular sieve and beta zeolite or mordenite. Above scheme allows the technical problem to be satisfactorily solved, and can be used in the industrial production of removing the nitrogen oxides from the tail gas discharged in the preparation of oxalate from CO
Description
Technical field
The present invention relates to the method that a kind of CO of removing prepares nitrogen oxide in the oxalate discharging tail gas, particularly about removing the method for nitrogen oxide in CO coupling system dimethyl oxalate or the diethy-aceto oxalate discharging tail gas.
Background technology
Oxalate is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extractant and various intermediate.Enter 21 century, oxalate is subjected to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the oxalate ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxalyl ammonia.Oxalate can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty acid ester, hexamethylene acetophenone, amido alcohol and many heterocyclic compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the oxalate 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 oxalate utilizes oxalic acid with alcohol esterification to take place and produces, production technology cost height, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking a process route 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 method.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 catalyst easily runs off in the course of reaction.The tool advantage of the vapor phase method of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase method 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 0.5MP, temperature is 80 ℃～150 ℃.
Be equipped with in the technology of dialkyl oxalate in carbon monoxide gas phase legal system; contain certain density alkyl nitrite and oxides of nitrogen gas in the discharge tail gas; these discharging gas that contain alkyl nitrite and nitrogen oxide directly enter atmosphere; pollute the environment; bring harm to human health; therefore must remove processing to the alkyl nitrite in the above-mentioned discharging gas and the gas of nitrogen oxide, make in the gas after the pollution abatement total content of alkyl nitrite and nitrogen oxide reach or be lower than the national environmental protection regulations of rules and allow emission standards.In the prior art, Japanese patent laid-open 11-315053 adopts methyl alcohol that the nitric oxide esterification is regenerated as methyl nitrite, absorbing methyl nitrite with methyl alcohol again reclaims the methyl nitrite in the gas, the raw material that the methyl nitrite that reclaims can be used as organic synthesis uses, this method is the large usage quantity of methyl alcohol on the one hand, because the methyl nitrite boiling point is lower, methyl nitrite be absorbed fully very difficulty.U.S. Pat 4879401 provides the method for removing nitrogen oxide foreign gas in a kind of alkyl nitrites preparation process, it adds low-level chain triacontanol in oxides of nitrogen gas, as methyl alcohol, ethanol, and oxygen, most nitrogen oxide will react and generate alkyl nitrite, the nitrogen oxide of residue small part, alkyl nitrite and other foreign gas adopt the low-level chain triacontanol cycles prepare, with the residual nitrogen oxygenate conversion is alkyl nitrite, and together with existing alkyl nitrite circular response, simultaneously, low-level chain triacontanol can be used as washing agent and removes foreign gas.But this method exists alkyl nitrite to handle halfway problem equally.
Summary of the invention
Technical problem to be solved by this invention is nitrogen oxide or the low technical problem of nitrites removal efficiency that in the past exists in the document, and a kind of new method that CO prepares nitrogen oxide in the oxalate discharging tail gas that removes is provided.This method has nitrogen oxide or the high advantage of nitrites removal efficiency.
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 CO of removing prepares the method for nitrogen oxide in the oxalate discharging tail gas, the discharging off-gas stream that will contain nitrogen oxide, in temperature is-20～100 ℃, pressure is 0.1～3.0MPa, and volume space velocity is 100～5000 hours
-1Condition under by adsorbent bed, contact with adsorbent, obtain removing the effluent of nitrogen oxide after the absorption; It is characterized in that adsorbent adopts at least a in ZSM type molecular sieve, 5A molecular sieve, β zeolite or the modenite.
In the technique scheme, the adsorbent bed operating condition is preferably: temperature is-10～60 ℃, and pressure is 0.1～2.0MPa, and volume space velocity is 300～3000 hours
-1Adsorbent is at least a in ZSM type molecular sieve, 5A molecular sieve preferably.
The discharging off-gas stream that contains nitrogen oxide in the technique scheme is from CO coupling system dimethyl oxalate or CO coupling system diethy-aceto oxalate discharging off-gas stream.
As everyone knows, in synthesis gas preparing ethylene glycol two-step method course of reaction, it is generally acknowledged by the CO coupling to make oxalate earlier that the technology path of oxalate repeated hydrogenation preparing ethylene glycol is the most feasible then.But, because the accumulation (as hydrogen and carbon dioxide) of inert gas can influence activity of such catalysts in the CO coupling reaction process, therefore, need discharging regularly, but what the problem that runs into was nitrites or nitrogen oxide to environment is very harmful, needs deep removal before discharging.The present inventor finds in research process, the off-gas stream that will contain nitrogen oxide and nitrites, under suitable condition, pass through specific adsorbent, can make nitrogen oxide and the absorption of nitrites component high selectivity in the off-gas stream, nitrogen oxide and nitrites constituent content are lower in the discharge tail gas, can reach discharge standard.
The present invention has made full use of nitrogen oxide and nitrites adsorptive selectivity, off-gas stream by will containing nitrogen oxide and nitrites is by being equipped with the adsorbent bed of adsorbent, the selection nitric oxide adsorption and the nitrites of high selectivity, significantly reduced the content of nitrogen oxide in the discharging tail gas or nitrites, reduced pollution environment.
Adopting technical scheme of the present invention, will contain the discharging off-gas stream of nitrogen oxide, is-20～60 ℃ in temperature, and pressure is 0.1～3.0MPa, and volume space velocity is 100～5000 hours
-1Condition under by the adsorbent bed of at least a adsorbent in ZSM type molecular sieve, 5A molecular sieve, β zeolite or the modenite is housed, contact with adsorbent, obtain removing the effluent of nitrogen oxide after the absorption, its result has obtained better technical effect for the content of nitrogen oxide in the absorption tail gas and nitrites can reach less than 10ppm.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
Take by weighing ZSM-5 adsorbent of molecular sieve 1000 grams, the internal diameter of packing into is in 50 millimeters the tubular reactor, with volume content be contain NO be 0.8% and methyl nitrite be 4% and the discharging tail gas of the nitrogen of surplus, be-10 ℃ in temperature, pressure is 0.1MPa, and volume space velocity is 500 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 6ppm in the emptying end gas, the content of methyl nitrite is 5ppm.
[embodiment 2]
Take by weighing ZSM-5 adsorbent of molecular sieve 1000 grams, the internal diameter of packing into is in 50 millimeters the tubular reactor, with volume content be contain NO be 2% and methyl nitrite be 2% and the discharging tail gas of the nitrogen of surplus, be-5 ℃ in temperature, pressure is 0.2MPa, and volume space velocity is 800 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 10ppm in the emptying end gas, the content of methyl nitrite is 6ppm.
[embodiment 3]
Take by weighing mordenite molecular sieve adsorbent 1000 grams, the internal diameter of packing into is in 50 millimeters the tubular reactor, with volume content be contain NO be 3% and methyl nitrite be 1% and the discharging tail gas of the nitrogen of surplus, be 5 ℃ in temperature, pressure is 0.4MPa, and volume space velocity is 1000 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 15ppm in the emptying end gas, the content of methyl nitrite is 8ppm.
[embodiment 4]
Take by weighing beta-zeolite molecular sieve adsorbent 1000 grams, the internal diameter of packing into is in 50 millimeters the tubular reactor, with volume content be contain NO be 0.5% and nitrous ether (ethyl nitrite) be 2% and the discharging tail gas of the nitrogen of surplus, be 10 ℃ in temperature, pressure is 0.8MPa, and volume space velocity is 2000 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 12ppm in the emptying end gas, the content of nitrous ether (ethyl nitrite) is 15ppm.
[embodiment 5]
Take by weighing 5A adsorbent of molecular sieve 1000 gram, the internal diameter of packing into is in 50 millimeters the tubular reactor, to be 10% with volume content for containing NO, propyl nitrite is 0.6%, and CO is 3% and the discharging tail gas of the nitrogen of surplus, is 40 ℃ in temperature, pressure is 2.0MPa, and volume space velocity is 3500 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 20ppm in the emptying end gas, the content of propyl nitrite is 18ppm.
[embodiment 6]
Take by weighing 5A adsorbent of molecular sieve 1000 gram, the internal diameter of packing into is in 50 millimeters the tubular reactor, to be 5% with volume content for containing NO, methyl nitrite is 0.2%, and CO is 5% and the discharging tail gas of the nitrogen of surplus, is 80 ℃ in temperature, pressure is 2.8MPa, and volume space velocity is 3000 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 25ppm in the emptying end gas, the content of methyl nitrite is 11ppm.
[embodiment 7]
Take by weighing ZSM-22 adsorbent of molecular sieve 1000 grams, the internal diameter of packing into is in 50 millimeters the tubular reactor, is 5% with volume content for containing NO, methyl nitrite is 0.2%, nitrous ether (ethyl nitrite) is 0.1% and the discharging tail gas of the nitrogen of surplus, in temperature is-10 ℃, and pressure is 2.0MPa, and volume space velocity is 2000 hours
-1Condition under adsorb by adsorbent bed, its absorption result is: the content of NO is 5ppm in the emptying end gas, the content of methyl nitrite is 10ppm, the content of nitrous ether (ethyl nitrite) is 5ppm.
[comparative example 1]
Form according to embodiment 6 identical discharging tail gas, just adopt the method C in the patent
2～C
4Alkanol replaces with methyl alcohol, and its result is the content 0 of nitrogen oxide in the emptying end gas, and the content of methyl nitrite is 1000ppm.
Obviously, the present invention has remarkable technique effect.
Claims (4)
1. one kind removes the method that CO prepares nitrogen oxide in the oxalate discharging tail gas, will contain the discharging off-gas stream of nitrogen oxide, is-20～100 ℃ in temperature, and pressure is 0.1～3.0MPa, and volume space velocity is 100～5000 hours
-1Condition under by adsorbent bed, contact with adsorbent, obtain removing the effluent of nitrogen oxide after the absorption; It is characterized in that adsorbent is selected from least a in ZSM type molecular sieve, 5A molecular sieve, β zeolite or the modenite.
2. prepare the method for nitrogen oxide in the oxalate discharging tail gas according to the described CO of removing of claim 1, it is characterized in that the adsorbent bed operating condition is: temperature is-10～60 ℃; Pressure is 0.1～2.0MPa; Volume space velocity is 300～3000 hours
-1
3. the method for preparing nitrogen oxide in the oxalate discharging tail gas according to the described CO of removing of claim 1 is characterized in that adsorbent is selected from least a in ZSM type molecular sieve or the 5A molecular sieve.
4. the method for preparing nitrogen oxide in the oxalate discharging tail gas according to the described CO of removing of claim 1 is characterized in that containing the discharging off-gas stream of nitrogen oxide from CO coupling system dimethyl oxalate or CO coupling system diethy-aceto oxalate discharging off-gas stream.
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| CN201010200011.6A CN102274671B (en) | 2010-06-11 | 2010-06-11 | Remove the method that CO prepares nitrogen oxide in oxalate emission |
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| CN201010200011.6A CN102274671B (en) | 2010-06-11 | 2010-06-11 | Remove the method that CO prepares nitrogen oxide in oxalate emission |
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| CN102274671B CN102274671B (en) | 2016-01-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599685A (en) * | 2013-11-18 | 2014-02-26 | 西南化工研究设计院有限公司 | Method for recycling nitrogen oxide in tail gas by means of production of oxalate with CO |
| CN104437028A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for removing alkyl nitrite and nitrous oxide from tail gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6030916A (en) * | 1997-03-10 | 2000-02-29 | Indian Petrochemicals Corp. Ltd. | Process for the preparation of a molecular sieve adsorbent for selectively adsorbing nitrogen from a gaseous mixture |
| CN101466467A (en) * | 2006-06-13 | 2009-06-24 | 丰田自动车株式会社 | Adsorbent for exhaust gas |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
-
2010
- 2010-06-11 CN CN201010200011.6A patent/CN102274671B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6030916A (en) * | 1997-03-10 | 2000-02-29 | Indian Petrochemicals Corp. Ltd. | Process for the preparation of a molecular sieve adsorbent for selectively adsorbing nitrogen from a gaseous mixture |
| CN101466467A (en) * | 2006-06-13 | 2009-06-24 | 丰田自动车株式会社 | Adsorbent for exhaust gas |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437028A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for removing alkyl nitrite and nitrous oxide from tail gas |
| CN103599685A (en) * | 2013-11-18 | 2014-02-26 | 西南化工研究设计院有限公司 | Method for recycling nitrogen oxide in tail gas by means of production of oxalate with CO |
| CN103599685B (en) * | 2013-11-18 | 2015-08-05 | 西南化工研究设计院有限公司 | Recycle the method for CO nitric oxide in tail gas for preparing oxalate |
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