CN1772600A - Production process of No gas for synthesizing oxalate - Google Patents
Production process of No gas for synthesizing oxalate Download PDFInfo
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- CN1772600A CN1772600A CN 200510107783 CN200510107783A CN1772600A CN 1772600 A CN1772600 A CN 1772600A CN 200510107783 CN200510107783 CN 200510107783 CN 200510107783 A CN200510107783 A CN 200510107783A CN 1772600 A CN1772600 A CN 1772600A
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Abstract
The production process of NO gas for synthesizing oxalate belongs to the field of chemical and environment protection technology. The production process includes ammoxidation of air to produce NOx as the NO gas for synthesizing oxalate, or utilizing the NOx in nitric acid producing tail gas as the NO gas for synthesizing oxalate, absorbing nitrite with alcohols and compression and condensation to recover alcohols and nitrite from the tail gas. The production process has liquid ammonia or gaseous ammonia of concentration 1-30 vol%, oxygen of concentration 1-30 vol%, alcohol concentration of 50-100 wt%, pressure of 0.1-10 MPa, and condensation temperature of -20 to 100 deg.c. The present invention has high economic utility and social utility.
Description
Technical field
The invention belongs to the technical field of chemical industry and environmental protection, it relates to the product with ammonia oxidation---and oxynitride is used as the novel method of the NO source of the gas that synthesis of oxalate uses.
Background technology
As everyone knows, the CO synthesis of oxalic ester by gaseous catalysis is contemporary C
1The most rising great novel process, the new technology of chemical research exploitation, its research and development success, can change the existing synthesis material route and the production process of synthesis of oxalate and important industrial chemicals such as oxalic acid, ethylene glycol, particularly can realize the strategic objective of " replacing oil ethene, indirect synthesizing glycol of two steps " with coal or Sweet natural gas, have great strategic importance, and can obtain good economic and social benefit.
In " continuous process for synthesis of oxalic ester by gaseous catalysis " reaction (ZL90101447.8), (see formula (1)), owing to after having introduced the catalytic promoter nitrous acid ester, the growing amount of reaction product is significantly improved.But building-up reactions is except that generating principal product---the barkite, in reaction end gas, can produce a large amount of NO gas simultaneously.For NO gas can constantly be reclaimed and recycle, generally all use oxygen (O
2) and alcohols and NO gas carry out oxidative esterification reaction (seeing formula (2)), the regeneration nitrous acid ester reclaims, recycle.But, when NO gas and oxygen and alcohols react, except generating the recycle and reuse of principal product nitrous acid ester, also often having side reaction formula (4), (5), (6) and take place, and have the rare nitric acid of by product to generate, this must consume many NO gases.Can stablize, for a long time, carry out continuously for the catalyzed reaction that makes synthesis of oxalate, just must constantly in reactive system, replenish NO gas.
At present, generally all be to use NaNO in the world
2With alcohols at H
2SO
4Effect is reacted the method that generates nitrous acid ester down, is used as replenishing of NO source of the gas.But this method can produce a large amount of by product Na
2SO
4, and cost is higher, only is adapted at using in a spot of research work in laboratory, can't satisfy the needs of large-scale industrial production.
With the technology of air ammonia oxidation generation oxynitride, be the very sophisticated industrial technology of preparation nitric acid, also be industrial current techique commonly used.But, up to the present, do not see oxynitride that useful ammonia oxidation takes place as yet and come directly report as the NO source of the gas of synthesis of oxalate, do not see that the nitrogen oxide that has in the direct use nitric acid industry tail gas is used as the report of the NO source of the gas of synthesis of oxalate yet.
Summary of the invention
The oxynitride that the objective of the invention is to directly take place with ammonia oxidation is used as the NO gas that the CO synthesis of oxalic ester by gaseous catalysis is used, and perhaps is used as the NO gas that the CO synthesis of oxalic ester by gaseous catalysis is used with the oxynitride in the nitric acid industry tail gas.
The oxynitride N that ammonia and air reaction generate
XO
Y(X=1,2; Y=1,2,3,4,5) concentration is 1～30
v%; Oxynitride N in the nitric acid industry tail gas
XO
Y(X=1,2; Y=1,2,3,4,5) concentration is 0.1～10
v%.The used ammonia of ammonia oxidation can be liquid ammonia or gaseous ammonia, and the concentration of ammonia is 1～30
v%.After the suitable heat exchange of these oxynitride processes, the alcohols reaction that directly enters esterification reaction tower and send into, generate nitrous acid ester, unreacted oxynitride enters oxidative esterification reaction tower and oxygen of sending into and alcohol reaction, continues to generate nitrous acid ester and a small amount of nitric acid.During directly with the oxynitride in the nitric acid industry tail gas, can save the step of ammonia oxidation and heat exchange, directly absorb and subsequent each step with alcohols.Used oxygen can be airborne oxygen or liquid oxygen or gaseous oxygen, and the concentration of oxygen is 1～30
v%.Used alcohols can be methyl alcohol or ethanol or propyl alcohol or butanols, and the concentration of alcohol is 50～100wt%.
Do like this, can reduce production costs greatly, consumption saves material.But the problem that also exists many needs to solve simultaneously.Because carry out oxidative ammonolysis with air, in the reaction product except having 5～30
vOutside the oxynitride about %, all the other are 95～70 years old
vThe component of % is N
2, Ar H
2Nonreactive gass such as O, and the concentration of the oxynitride in the nitric acid industry tail gas is lower, generally only has 0.1～10
vAbout %, other are 99.9～90 years old
v% is N
2, Ar H
2Nonreactive gass such as O.If allow these nonreactive gass enter the synthesis of oxalate reactive system in a large number, very unfavorable to the reaction of catalysis synthesis of oxalate, even reaction can't be carried out.Have only these nonreactive gass are discharged reactive system, could guarantee that successful reaction carries out.And work as these N
2, Ar H
2When nonreactive gass such as O are discharged reactive system, can take reactive material useful in the synthesis reaction system such as NO, RONO and alcohols simultaneously out of, both waste starting material, pollute the environment again.Therefore, must NO, RONO and alcohols reclaims and the processing of decontamination environment.
We are that the method that adopts compression and condensation to combine is finished this work in CN1048098A.But do like that, the operational condition of requirement is relatively harsher.We absorb a large amount of nitrous acid ester with alcohols earlier now, and then with compression and the method that combines of condensation, a spot of alcohols and nitrous acid ester in the gas phase are condensed into liquid, used pressure is at 0.1～10Mpa, used condensing temperature is between-20 ℃～100 ℃, alcohols and nitrous acid ester and the non-gas that coagulates are separated, reclaim condensed fluid then and recycle, discharge the non-gas that coagulates.Do like this, both recyclable alcohols and nitrous acid ester can reach the purpose of eliminating the nitrogen oxides pollution environment again, make this technological process more rationally with perfect.
Advantage of the present invention is, both can provide a large amount of necessary NO gases for the CO continuous process for synthesis of oxalic ester by gaseous catalysis, reduce production costs, can fully reclaim useful reactant in the non-gas with fixed attention of discharging again, reach the purpose that reduces alcohols consumption and eliminate the nitrogen oxides pollution environment.The present invention can be the CO continuous process for synthesis of oxalic ester by gaseous catalysis and uses industrial CO gas and industrial NO gas to create favorable conditions on a large scale, has good economic benefits and social benefit.
Description of drawings
Accompanying drawing is a process flow diagram, and wherein A is a converter for ammonia oxidation; B is an interchanger; C is an esterification reaction tower; D is the oxidative esterification reaction tower; E is a compressor; F is the ester absorption tower; G is a round trip condensation separation tower; H is a receiving tank; I is an alcohol solution cerumen jar.
Embodiment
Existing combined process schematic flow sheet is described the specific embodiment of the present invention in detail: air and ammonia are directly sent into converter for ammonia oxidation A carry out oxidizing reaction, after the oxynitride that generates cools off through interchanger B, the alcohols reaction that directly enters esterification reaction tower C and send into generates nitrous acid ester; Unreacted oxynitride carries out oxidative esterification reaction at oxidative esterification reaction tower D and an amount of oxygen of sending into and alcohols (can be methyl alcohol or ethanol or propyl alcohol or butanols), oxynitride is all reacted generate nitrous acid ester and a small amount of nitric acid; Then, allow gas through compressor E, pressure P is 0.1MPa～10MPa, enter alcohols absorption tower F again, the nitrous acid ester that allows alcohols absorb generate, and then enter round trip condensing tower G is under-20 ℃～100 ℃ and P=0.1～10MPa condition, non-nitrous acid ester and the alcohols condensation liquefaction that coagulates in the gas, and and N
2, uncondensable gas such as Ar separates.Condensation liquefaction nitrous acid ester and alcohols enter receiving tank H, recycling use; N
2, uncondensable gas such as Ar discharges reactive system emptying from pipeline.Do like this, can efficient recovery nitrous acid ester and alcohols, can reach the purpose of eliminating the nitrogen oxides pollution environment again.
Claims (6)
1, the production method of the NO gas used of a kind of synthesis of oxalate is characterized in that: the oxynitride N that generates with ammonia and air reaction
XO
YBe used as the NO gas that synthesis of oxalate is used, X=1,2 wherein, Y=1,2,3,4,5; This oxynitride N
XO
YConcentration be 1～30V%.
2, the production method of the NO gas used of synthesis of oxalate as claimed in claim 1 is characterized in that: described oxynitride N
XO
YDirectly use the oxynitride N in the industrial tail gas body of producing nitric acid
XO
Y, X=1,2 wherein, Y=1,2,3,4,5; This oxynitride N
XO
YConcentration be 0.1～10V%.
3, the production method of the NO gas used of synthesis of oxalate as claimed in claim 1 or 2, it is characterized in that: in described method, absorb nitrous acid ester with alcohols, the temperature of alcohols is-20 ℃～100 ℃, the pressure that absorbs is 0.1～10MPa, used alcohols is methyl alcohol or ethanol or propyl alcohol or butanols, and its pure concentration is at 50～100wt%.
4, the production method of the NO gas used of synthesis of oxalate as claimed in claim 1 or 2, it is characterized in that: in described method, combine and eliminate the method for nitrogen oxides pollution environment in the non-with fixed attention gas of discharging with compression and condensation, used pressure is 0.1～10MPa, and used condensing temperature is at-20 ℃～100 ℃.
5, the production method of the NO gas used of synthesis of oxalate as claimed in claim 1 or 2, it is characterized in that: used oxygen is airborne oxygen or liquid oxygen or gaseous oxygen, and the concentration of its oxygen is at 1～30V%.
6, the production method of the NO gas used of synthesis of oxalate as claimed in claim 1, it is characterized in that: used ammonia is liquid ammonia or gaseous ammonia, the concentration of its ammonia is 1～30V%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101077834A CN100513304C (en) | 2005-09-30 | 2005-09-30 | Production process of No gas for synthesizing oxalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101077834A CN100513304C (en) | 2005-09-30 | 2005-09-30 | Production process of No gas for synthesizing oxalate |
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| Publication Number | Publication Date |
|---|---|
| CN1772600A true CN1772600A (en) | 2006-05-17 |
| CN100513304C CN100513304C (en) | 2009-07-15 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN101993363B (en) * | 2009-08-31 | 2013-06-05 | 中国石油化工股份有限公司 | Method for preparing oxalic ester by CO coupling |
| CN101993366B (en) * | 2009-08-31 | 2014-01-22 | 中国石油化工股份有限公司 | Method for preparing oxalate by using CO gaseous phase process |
| US8871968B2 (en) | 2010-04-15 | 2014-10-28 | China Petroleum & Chemical Corporation | Process of producing oxalate by CO gas phase method |
| US8921592B2 (en) | 2010-06-11 | 2014-12-30 | China Petroleum & Chemical Corporation | Process of producing oxalate by CO gas phase method |
-
2005
- 2005-09-30 CN CNB2005101077834A patent/CN100513304C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993363B (en) * | 2009-08-31 | 2013-06-05 | 中国石油化工股份有限公司 | Method for preparing oxalic ester by CO coupling |
| CN101993366B (en) * | 2009-08-31 | 2014-01-22 | 中国石油化工股份有限公司 | Method for preparing oxalate by using CO gaseous phase process |
| US8871968B2 (en) | 2010-04-15 | 2014-10-28 | China Petroleum & Chemical Corporation | Process of producing oxalate by CO gas phase method |
| US8921592B2 (en) | 2010-06-11 | 2014-12-30 | China Petroleum & Chemical Corporation | Process of producing oxalate by CO gas phase method |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN102267921B (en) * | 2011-05-26 | 2016-02-24 | 陈贻盾 | A kind of synthesis oxamide continuous processing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100513304C (en) | 2009-07-15 |
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Effective date of registration: 20080926 Address after: Inner Mongolia Tongliao Tongliao economic and Technological Development Zone Administrative office building, 6 floor Applicant after: Tongliao Gold Coal Chemical Co., Ltd. Address before: Fuzhou City, Fujian Province, Yangqiao Road No. 155 Applicant before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |
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