CN102079710A - Safe method for preparing nitropropane by vapor-phase nitration - Google Patents
Safe method for preparing nitropropane by vapor-phase nitration Download PDFInfo
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- CN102079710A CN102079710A CN2010105924084A CN201010592408A CN102079710A CN 102079710 A CN102079710 A CN 102079710A CN 2010105924084 A CN2010105924084 A CN 2010105924084A CN 201010592408 A CN201010592408 A CN 201010592408A CN 102079710 A CN102079710 A CN 102079710A
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Abstract
The invention relates to a safe method for preparing nitropropane by vapor-phase nitration, which comprises the following steps: carrying out reaction in a single-channel reactor, wherein after the reaction material propane enters a preheating pipe via a flowmeter and is mixed with pumped nitric acid in a mixing pipe, the mixed materials are sent into a reaction pipe, and the mol ratio of the propane to the nitric acid is controlled at (1-8):1; the mixed materials are subjected to nitration reaction by mass transfer and heat transfer in the reaction pipe, and the products enter a separator; and the reaction products stand in the separator until the reaction products stratify, the organic phase is separated from the water phase, and the organic phase is washed and dried to obtain the product. By using the invention, the propane and the nitric acid can be directly synthesized into various nitroparaffins under the condition of no catalyst, and the process is safe and continuous. The mass transfer and heat transfer are completed in the single channel without additional heat dissipation, thereby reducing the power consumption. The invention has the advantage of simple structure and is easy to operate. The conversion rate of the propane is higher than 20%, and the selectivity of the nitropropane is higher than 80%.
Description
Technical field
A kind of alkane vaporphase nitration that the present invention relates to prepares the technology of nitroparaffins, and relating in particular to a kind of is raw material with propane and nitric acid, the method for safe vaporphase nitration system nitropropane in single pass reactor.
Background technology
Propane is nitrated to be important reaction in the chemical industry, and its product has Nitromethane 99Min., nitroethane, 1-nitropropane and 2-nitropropane.Nitroparaffins are as important fine chemicals, it is the critical materials of a lot of high added value medicine intermediates and chemical reagent, nitropropane is Synthetic 2-aminoisobutanol, 2-dimethylamino-2-methyl-1-propanol, N-isopropylhydroxyla and 4, the critical materials of 4-dimethyl oxazoline quinoline etc.The development of fine chemistry industry, the nitrated development of technology of alkane is its guarantee.
Alkane is nitrated to be to introduce nitro on the organic carbon atom, belongs to strong exothermal reaction.The propane nitration processes mainly contains two kinds: a kind of is the nitric acid direct oxidation method, is representative with U.S. solvent company, and its patent US 2905724 is a purpose to produce multiple low-carbon (LC) nitroparaffins.4 operations such as that whole process is divided is nitrated, product reclaims, raw material propane reclaims with nitric acid, nitroparaffins separate and make with extra care.Nitration reaction is finished in adiabatic reactor, 350～400 ℃ of temperature, pressure 1.0～1.2Mpa, the residence time is 1.0～1.2s, and when being raw material with propane, product roughly contains Nitromethane 99Min. 25%, nitroethane 15%, 1-nitropropane 20%, 2-nitropropane 40%.Look raw material and reaction conditions and different, depend primarily on the formation of low-carbon alkanes in the raw material.The transformation efficiency of propane and nitric acid is respectively 10% and 98%, and selectivity is respectively 60% and 38%.Another kind is the nitrogen oxide nitrofication process, and by the exploitation of French GP company, mentioning with low-carbon alkanes and nitrogen oxide in patent FR1390523 is main raw material, introduces oxygen enrichment or air oxidant, 280～340 ℃ of temperature of reaction, pressure 1.0～1.2MPa, residence time 10s.As C3H8: NO2: during air=61: 14.5: 24.5, product contains Nitromethane 99Min. 15%, nitroethane 5%, 1-nitropropane 20%, 2-nitropropane 60%.This technology has been cancelled the nitric acid recovery system, shortened the nitration reaction technical process, but owing to need introducing air, reactive system might be in the limits of explosion edge at any time, security is relatively poor, and the transformation efficiency of low-carbon alkanes and nitrogen oxide and selectivity all are lower than nitric acid nitrating technology.
Above publication fails to solve fully nitrated safety issue, and conversion of propane and nitropropane selectivity also have much room for improvement.
Summary of the invention
The object of the present invention is to provide a kind of method of safe vaporphase nitration system nitropropane, specific surface area and length-to-diameter ratio by the control single pass reactor, efficiently solve the heat dissipation problem of traditional nitrator, nitrated temperature is along the axial uniform distribution of reaction single passage, make nitration reaction carry out more fully, effectively restrain or reduce the generation of side reaction.Improve conversion of propane and nitropropane selectivity, eliminate the potential safety hazard in the nitration reaction.
A kind of method of safe vaporphase nitration system nitropropane, in single pass reactor, react, reaction mass propane enters preheating pipe via under meter, sends into reacting pipe with the nitric acid that pumps into after mixing duct mixes, control propane and nitric acid mol ratio 1～8: 1; Mixture is realized mass transfer, heat transfer in reacting pipe, finish nitration reaction, and product enters separator; With the reaction product standing demix in the separator, separate organic phase and water, organic phase obtains product Nitromethane 99Min., nitroethane, 1-nitropropane and 2-nitropropane through washing drying.
In the nitrifying process of the present invention, used nitric acid is nitrating agent, and concentration of nitric acid is greater than 50wt%.
Single pass reactor of the present invention comprises one section reacting pipe 1 at least, one section mixing duct 2 and one section preheating pipe 3, be three ports 4 between the pipeline 2 and 3, each pipeline adopts series system to connect, and the volume ratio between each pipeline is 1: 0.5～0.8: 0.5～0.8.
The nitration reaction internal diameter of the pipeline is 2～20mm, and length is 100～6000mm, and length-to-diameter ratio (L/D) is 100～600: 1, and specific surface area (S/V) is 0.1～2.
Preheating temperature in the nitrated preheating pipe is 300 ℃～400 ℃.
Mixing temperature in the nitrated mixing duct is 200 ℃～280 ℃.
Temperature of reaction in the nitration reaction pipeline is 350 ℃～500 ℃.
The working pressure that carries out nitration reaction in single pass reactor is 0～1.0Mpa.
The beneficial effect that technical solution of the present invention realizes:
1, directly synthetic multiple nitroparaffins under propane and the nitric acid catalyst-free situation, the process safe and continuous;
2, mass transfer, heat transfer are finished in single passage, need not extra heat dissipation, reduce power consumption;
3, simple in structure, easy handling;
4, suitable specific surface area and length-to-diameter ratio are controlled, and realize that easily isothermal is nitrated, and conversion of propane is greater than 20%, and the nitropropane selectivity is greater than 80%.
Description of drawings
Fig. 1 is the single pass reactor structural representation.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with accompanying drawing.Below implement to be intended to illustrate the present invention rather than limitation of the present invention.
As shown in Figure 1, the present invention adopts single pass reactor to carry out nitrated system nitropropane.Reacting pipe internal diameter 4mm, long 1000mm, length-to-diameter ratio 250: 1, specific surface area 0.82, reacting pipe 1 volume: mixing duct 2 volumes: preheating pipe 3 volumes=1: 0.6: 0.6.The mole proportioning of propane and 65wt% nitric acid is 4: 1, working pressure 0.1Mpa, and propane enters preheating pipe 3 through under meter, 350 ℃ of preheating temperatures, nitric acid pumps into three ports 4 through volume pump, and 250 ℃ of mixing temperatures, material enter reacting pipe 1 behind the thorough mixing in mixing duct 2,440 ℃ of temperature of reaction, residence time 0.8s, reaction 1h, product layering after the separator condensation, the upper strata is an organic phase, lower floor's water.The upper strata with chromatogram ration analysis after, the transformation efficiency that adopts material balance to calculate propane again is 21.1%, the nitropropane selectivity is 82.6%.
Process and reactor used with embodiment 1, difference are that propane and nitric acid mole proportioning are 2: 1, working pressure 0.5Mpa, and residence time 1.4s. conversion of propane is 22.3%, the nitropropane selectivity is 81.7%.
Process and reactor used with embodiment 1, difference are, 200 ℃ of mixing temperatures, 300 ℃ of preheating temperatures, 435 ℃ of temperature of reaction.Conversion of propane is 20.8%, and the nitropropane selectivity is 84.4%.
Embodiment 4
Process is with embodiment 1, and difference is, reacting pipe internal diameter 20, long 6000mm, length-to-diameter ratio 300: 1, specific surface area 0.2, reacting pipe volume: mixing duct volume: preheating pipe volume=1: 0.5: 0.5.400 ℃ of temperature of reaction, residence time 1.5s.Conversion of propane is 24%, and the nitropropane selectivity is 81.03%.
Claims (9)
1. the method for a safe vaporphase nitration system nitropropane, it is characterized in that in single pass reactor, reacting, reaction mass propane enters preheating pipe via under meter, sends into reacting pipe with the nitric acid that pumps into after mixing duct mixes, control propane and nitric acid mol ratio 1～8: 1; Mixture is realized mass transfer, heat transfer in reacting pipe, finish nitration reaction, and product enters separator; With the reaction product standing demix in the separator, separate organic phase and water, organic phase obtains product through washing drying.
2. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that described nitric acid is nitrating agent, and concentration is greater than 50wt%.
3. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that described reacting pipe, and the volume ratio of described mixing duct and described preheating pipe is 1: 0.5～0.8: 0.5～0.8.
4. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that described reacting pipe length-to-diameter ratio is 100～600: 1.
5. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that described reacting pipe specific surface area is 0.1～2.
6. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that the preheating temperature in the described preheating pipe is 300 ℃～400 ℃.
7. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that the mixing temperature in the described mixing duct is 200 ℃～280 ℃.
8. the method for safe vaporphase nitration system nitropropane according to claim 1 is characterized in that the temperature of reaction in the described reacting pipe is 350 ℃～500 ℃.
9. the method for safe vaporphase nitration system nitropropane according to claim 1, the working pressure that it is characterized in that carrying out nitration reaction in described single pass reactor is 0～1.0Mpa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010592408 CN102079710B (en) | 2010-12-09 | 2010-12-09 | Safe method for preparing nitropropane by vapor-phase nitration |
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| CN 201010592408 CN102079710B (en) | 2010-12-09 | 2010-12-09 | Safe method for preparing nitropropane by vapor-phase nitration |
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| CN102079710A true CN102079710A (en) | 2011-06-01 |
| CN102079710B CN102079710B (en) | 2013-05-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003885A (en) * | 2014-03-25 | 2014-08-27 | 嘉兴润博化工科技有限公司 | Preparing method of low-carbon nitroparaffins |
| CN107325000A (en) * | 2017-06-12 | 2017-11-07 | 嘉兴润博化工科技有限公司 | A kind of method that alkali metal catalyzed gas nitrification prepares nitroparaffins |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489320A (en) * | 1949-11-29 | Nitration of paraffins | ||
| EP0402207A2 (en) * | 1989-06-08 | 1990-12-12 | Sumitomo Chemical Company, Limited | Process for producing nitro-benzenes |
| CN101613285A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of oil of mirbane synthetic method and equipment special |
-
2010
- 2010-12-09 CN CN 201010592408 patent/CN102079710B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489320A (en) * | 1949-11-29 | Nitration of paraffins | ||
| EP0402207A2 (en) * | 1989-06-08 | 1990-12-12 | Sumitomo Chemical Company, Limited | Process for producing nitro-benzenes |
| CN101613285A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of oil of mirbane synthetic method and equipment special |
Non-Patent Citations (1)
| Title |
|---|
| H.J.HIBSHMAN等: "Nitration of Ethane", 《INDUSTRIAL AND ENGINEERING CHEMISTRY》, vol. 32, no. 3, 31 March 1940 (1940-03-31), pages 427 - 429 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003885A (en) * | 2014-03-25 | 2014-08-27 | 嘉兴润博化工科技有限公司 | Preparing method of low-carbon nitroparaffins |
| CN107325000A (en) * | 2017-06-12 | 2017-11-07 | 嘉兴润博化工科技有限公司 | A kind of method that alkali metal catalyzed gas nitrification prepares nitroparaffins |
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| CN102079710B (en) | 2013-05-29 |
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Effective date of registration: 20190326 Address after: 314000 Building No. 1, 778 Asia-Pacific Road, Jiaxing City, Zhejiang Province Co-patentee after: Jiaxing Borun Chemical Technology Co., Ltd. Patentee after: Jiaxing Green Chemistry Engineering Center, Chinese Academy of Sciences Co-patentee after: TENGZHOU NEW MATERIAL TECHNOLOGY CO., LTD. Address before: 314000 Building No. 1, 778 Asia-Pacific Road, Jiaxing City, Zhejiang Province Co-patentee before: Jiaxing Borun Chemical Technology Co., Ltd. Patentee before: Jiaxing Green Chemistry Engineering Center, Chinese Academy of Sciences |
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