CN102219695A - Manufacturing method of C1-C4 alkyl nitrites - Google Patents
Manufacturing method of C1-C4 alkyl nitrites Download PDFInfo
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- CN102219695A CN102219695A CN2010101469899A CN201010146989A CN102219695A CN 102219695 A CN102219695 A CN 102219695A CN 2010101469899 A CN2010101469899 A CN 2010101469899A CN 201010146989 A CN201010146989 A CN 201010146989A CN 102219695 A CN102219695 A CN 102219695A
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Abstract
The invention relates to a manufacturing method of C1-C4 alkyl nitrites, which mainly solves a technical problem of low selectivity of a target product alkyl nitrite in the prior art. In the invention, the problem is preferably solved by using the following technical scheme: raw materials of nitric oxide, oxygen and C1-C4 alkanol respectively enter a rotating packed bed reactor and contact and react with each other on a rotating packing of the rotating packed bed reactor to generate an effluent containing C1-C4 alkyl nitrites under conditions of reaction temperature of 0-150 DEG C, reaction pressure of -0.09 MPa to 1.5 MPa, mol ratio of (1-100):1 between the C1-C4 alkanol and the nitric oxide and mol ratio of (4-50):1 between the nitric oxide and the oxygen. The manufacturing method of the C1-C4 alkyl nitrites, provided by the invention, can be used in the industrial production of increasing the yield of the C1-C4 alkyl nitrites.
Description
Technical field
The present invention relates to a kind of C
1～C
4The production method of alkyl nitrous acid ester is particularly about the required C of CO coupling producing oxalic ester
1～C
4The production 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 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 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 C
1～C
4The production method of alkyl nitrous acid ester.This method 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 used in the present invention is as follows: a kind of C
1～C
4The production method of alkyl nitrous acid ester is with oxynitride, oxygen and C
1～C
4Alkanol feedstock enters rotary packed bed reactor respectively, is 0～150 ℃ in temperature of reaction, and reaction pressure is-0.09～1.5MPa, C
1～C
4Alkanol is 1～100: 1 with the ratio of the mole number of oxynitride, and oxynitride is under 4～50: 1 condition with the ratio of the mole number of oxygen, and contact reacts on the rotation filler of rotary packed bed reactor generates and contains C
1～C
4The effluent of alkyl nitrous acid ester; Wherein, used rotary packed bed reactor, comprise rotary packed bed reactor shell (8), first gas inlet (1), rotation filler (2), fluid inlet (4) and liquid distributor (9), it is characterized in that rotary packed bed reactor shell (8) goes up second gas inlet (10) in addition, rotation filler (2) is fixed on the motor shaft (11), and the bottom of rotary packed bed reactor shell (8) is provided with liquid outlet (7).
Oxynitride is preferably from NO, N in the technique scheme
2O
3Or NO
2In one or more mixed gas, contain NO in the described oxynitride, the NO mole number is greater than NO
2Mole number.The reaction conditions preferable range is in the rotary packed bed reactor: temperature of reaction is 10～100 ℃, and reaction pressure is-0.05～1.0MPa, C
1～C
4Alkanol is 1～50: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～20: 1 with the ratio of the mole number of oxygen; Reaction conditions more preferably scope is: temperature of reaction is 10～60 ℃, and reaction pressure is-0.05～0.8MPa, C
1～C
4Alkanol is 1～20: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～10: 1 with the ratio of the mole number of oxygen.
The rotating speed of the rotation filler of rotary packed bed reactor 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.
C in the technique scheme
1～C
4The production method of alkyl nitrous acid ester, two gas inletes in first gas inlet and second gas inlet are set on the rotary packed bed reactor wherein, enter oxynitride and oxygen respectively, can avoid oxygen that a gas inlet brings and NO to be pre-mixed and cause N
2O
4The side reaction aggravation that too much generates and cause.
C of the present invention
1～C
4The production method of alkyl nitrous acid ester, on the basis of the characteristics of fully studying oxynitride and oxygen and alcohol generation oxidative esterification reaction, propose to adopt rotary packed bed reactor as reactor, make full use of the significant advantage that can how much orders of magnitude significantly improves gas-liquid mass transfer speed of rotary packed bed reactor, and then effectively promote main reaction, the draw up generation of side reaction, thus utilization ratio of raw materials such as NO improved, greatly improved the selectivity of nitrous acid ester.
C of the present invention
1～C
4The production method of alkyl nitrous acid ester 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.Two gas inletes is provided with the pre-mixing that can avoid oxynitride and oxygen and the N that causes in the rotary packed bed reactor of while
2O
4Generation, and then significantly improve the selectivity of alkyl nitrous acid ester.
Description of drawings
Fig. 1 is C
1～C
4The reactor flow process figure of the production method of alkyl nitrous acid ester
The rotary packed bed reactor shell 9-liquid distributor of the 1-first gas inlet 2-rotation filler 3-pneumatic outlet 4-fluid inlet 5-fluid inlet pipeline 6-liquid outlet pipeline 7-liquid outlet 8-10-second gas inlet 11-motor shaft among the figure.
Embodiment
Below in conjunction with accompanying drawing to C of the present invention
1～C
4The reactor of the production method of alkyl nitrous acid ester elaborates.
Rotary packed bed reactor among the present invention, adopt rotary packed bed reactor shell 8, first gas inlet 1, rotation filler 2, fluid inlet 4 and liquid distributor 9, also has second gas inlet 10 on the wherein rotary packed bed reactor shell 8, rotation filler 2 is fixed on the motor shaft 11, and the bottom of rotary packed bed reactor shell 8 is provided with liquid outlet 7.In rotary packed bed reactor fluid inlet 4 pipelines liquid distributor 13 is set, is mainly used in the uniform distribution of liquid.
Two gas inletes of the reactor among the present invention enter oxides of nitrogen gas raw material and oxygen respectively, and fluid inlet 4 enters C
1～C
4Alkyl alcohol.Rotation filler power motor preferably adopts frequency control motor.
During work with gas, oxygen and the C of nitrogen-containing oxide
1～C
4Alkyl alcohol is introduced in the rotary packed bed reactor rotation filler 2 from first gas inlet 1, second gas inlet 10 and fluid inlet 4 respectively, and 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 introduced the fluid inlet 4 of rotary packed bed reactor by fluid inlet pipeline 5 and is entered liquid distributor 9 and rotation filler 2, and gas, liquid fully contact in the rotation filler, and the way of contact adopts adverse current, cross-flow all can.Nitrogenous compound in the gas and oxygen and C
1～C
4Alkyl alcohol contains C through after reacting
1～C
4Alkyl nitrous acid ester gas is discharged by venting port 3, and reacted liquid is discharged by fluid pipeline 6 by the liquid outlet 7 of rotary packed bed reactor.
The rotating speed of rotation filler is 100～10000rpm in the above-mentioned commentaries on classics bed of packings, 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.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
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 12%v, the gas volume 2m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 2000rpm.Methanol solution is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, methanol solution mol ratio are 1: 30 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 20 ℃, and pressure is-0.05MPa, 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 23%v, the gas volume 4m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 4000rpm.Methanol solution is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, methanol solution mol ratio are 1: 10 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 30 ℃, and pressure is 0.01MPa, 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, the gas volume 2.5m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 6000rpm.Methanol solution is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, methanol solution mol ratio are 1: 50 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 40 ℃, and pressure is-0.03MPa, and its result is, the selectivity of methyl nitrite is 99.70%, and the transformation efficiency of oxygen is 100%.
[embodiment 4]
The gas volume of first gas of nitrogen-containing oxide raw material is 1000m
3/ h, wherein, the concentration of NO is 30%v, the gas volume 40m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 2000rpm.Ethanolic soln is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, ethanol liquid mol ratio are 1: 10 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 40 ℃, and pressure is 0.1MPa, 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 9%v, the gas volume 20m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 1000rpm.Propanol solution is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, propyl alcohol liquid mol ratio are 1: 10 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 50 ℃, and pressure is 0.3MPa, 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, the gas volume 8m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 2000rpm.Methanol solution is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, methanol solution mol ratio are 1: 5 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 30 ℃, and pressure is 1.2MPa, 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 5%v, the gas volume 5m of the second gas oxygen
3/ h, two kinds of gases enter rotary packed bed reactor 8 from first gas inlet 1 and second gas inlet 10 respectively, under differential pressure action, diffuse into rotation filler 2, and rotation filler rotating speed transfers to 3000rpm.Methanol solution is introduced fluid inlet 4 by the fluid inlet pipeline 5 of rotary packed bed reactor, and enter liquid distributor 9 and spray to the filler inboard, oxynitride, methanol solution mol ratio are 1: 5 in the gas, gas and liquid counter current contact in filler, 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 the pneumatic outlet 3 of rotary packed bed reactor, and liquid efflunent II discharges by fluid pipeline 6 through liquid outlet 7.Temperature of reaction is 40 ℃, and pressure is 0.01MPa, and its result is, the selectivity of methyl nitrite is 99.73%, and the transformation efficiency of oxygen is 100%.
Claims (5)
1. C
1～C
4The production method of alkyl nitrous acid ester is with oxynitride, oxygen and C
1～C
4Alkanol feedstock enters rotary packed bed reactor respectively, is 0～150 ℃ in temperature of reaction, and reaction pressure is-0.09～1.5MPa, C
1～C
4Alkanol is 1～100: 1 with the ratio of the mole number of oxynitride, and oxynitride is under 4～50: 1 condition with the ratio of the mole number of oxygen, and contact reacts on the rotation filler of rotary packed bed reactor generates and contains C
1～C
4The effluent of alkyl nitrous acid ester; Wherein, used rotary packed bed reactor, comprise rotary packed bed reactor shell (8), first gas inlet (1), rotation filler (2), fluid inlet (4) and liquid distributor (9), it is characterized in that rotary packed bed reactor shell (8) goes up second gas inlet (10) in addition, rotation filler (2) is fixed on the motor shaft (11), and the bottom of rotary packed bed reactor shell (8) is provided with liquid outlet (7).
2. according to the described C of claim 1
1～C
4The production method of alkyl nitrous acid ester is characterized in that oxynitride is selected from NO, N
2O
3Or NO
2In one or more mixed gas, contain NO in the described oxynitride, the NO mole number is greater than NO
2Mole number.
3. according to the described C of claim 1
1～C
4The production method of alkyl nitrous acid ester is characterized in that temperature of reaction is 10～100 ℃, and reaction pressure is-0.05～1.0MPa, C
1～C
4Alkanol is 1～50: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～20: 1 with the ratio of the mole number of oxygen.
4. according to the described C of claim 3
1～C
4The production method of alkyl nitrous acid ester is characterized in that temperature of reaction is 10～60 ℃, and reaction pressure is-0.05～0.8MPa, C
1～C
4Alkanol is 1～20: 1 with the ratio of the mole number of oxynitride, and oxynitride is 4～10: 1 with the ratio of the mole number of oxygen.
5. according to the described C of claim 1
1～C
4The production method of alkyl nitrous acid ester is characterized in that in rotary packed bed reactor fluid inlet (4) pipeline liquid distributor (13) being set.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101469899A CN102219695B (en) | 2010-04-15 | 2010-04-15 | Manufacturing method of C1-C4 alkyl nitrites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101469899A CN102219695B (en) | 2010-04-15 | 2010-04-15 | Manufacturing method of C1-C4 alkyl nitrites |
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| Publication Number | Publication Date |
|---|---|
| CN102219695A true CN102219695A (en) | 2011-10-19 |
| CN102219695B CN102219695B (en) | 2013-12-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114887569A (en) * | 2022-05-23 | 2022-08-12 | 南通富莱克流体装备有限公司 | Gas-liquid-solid supergravity reinforced reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0023745B1 (en) * | 1977-12-01 | 1985-05-08 | Imperial Chemical Industries Plc | Process and apparatus for effecting mass transfer |
| US4879401A (en) * | 1987-09-29 | 1989-11-07 | Union Carbide Chemicals And Plastics Company Inc. | Process for removal of impurities in alkyl nitrite formation |
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| CN1830526A (en) * | 2006-02-17 | 2006-09-13 | 中北大学 | Purification technology and equipment of waste gas containing high concentration nitrogen oxide |
-
2010
- 2010-04-15 CN CN2010101469899A patent/CN102219695B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0023745B1 (en) * | 1977-12-01 | 1985-05-08 | Imperial Chemical Industries Plc | Process and apparatus for effecting mass transfer |
| US4879401A (en) * | 1987-09-29 | 1989-11-07 | Union Carbide Chemicals And Plastics Company Inc. | Process for removal of impurities in alkyl nitrite formation |
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| CN1830526A (en) * | 2006-02-17 | 2006-09-13 | 中北大学 | Purification technology and equipment of waste gas containing high concentration nitrogen oxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114887569A (en) * | 2022-05-23 | 2022-08-12 | 南通富莱克流体装备有限公司 | Gas-liquid-solid supergravity reinforced reactor |
| CN114887569B (en) * | 2022-05-23 | 2023-10-03 | 南通富莱克流体装备有限公司 | Gas-liquid-solid supergravity reinforced reactor |
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|---|---|
| CN102219695B (en) | 2013-12-25 |
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