CN107793316A - A kind of method of microreactor synthesis methyl nitrite - Google Patents
A kind of method of microreactor synthesis methyl nitrite Download PDFInfo
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- CN107793316A CN107793316A CN201711271225.0A CN201711271225A CN107793316A CN 107793316 A CN107793316 A CN 107793316A CN 201711271225 A CN201711271225 A CN 201711271225A CN 107793316 A CN107793316 A CN 107793316A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of microreactor synthesis methyl nitrite, it is mainly characterized by：(a) NO and O2The pre-reaction first in shell and tube reactor, generates mixed gas (b) mixed gas containing oxynitrides and methanol carries out nitration reaction in micropassage type reactor (single channel or multichannel), generates methyl nitrite.The hydraulic diameter of micro- reaction channel is located at 100~3000 micrometer ranges, and gas phase air speed is 2000~50000h in microreactor‑1, N2 contents 40~70%, NO and O in gas phase2Volume ratio 4~7, methanol and charging NO mol ratios 1~2, have reacted product methyl nitrite and have been based on O2Yield be more than 70%.The reaction process residence time of material is short, and side reaction is effectively suppressed, and reduces HNO3Deng generation, equipment is perishable.Meanwhile the characteristics of being conducted heat using micro passage reaction efficient mass transfer, technique have preferably operability and security.
Description
Technical field
The present invention relates to a kind of synthetic method of methyl nitrite, specially nitrous acid is continuously synthesized using microreactor
Methyl esters.
Background technology
Ethylene glycol is as a kind of important Organic Chemicals, mainly for the production of polyester fiber, plastics and rubber etc.,
It is widely used in solvent, lubricant, plasticizer and antifreezing agent etc..Larger breach be present in the supply of China ethylene glycol, import according to
Degree of depositing is up to 70%, and is mainly derived from the Middle East and North America.In view of the solid demand of polyester industrial, it is contemplated that following China's ethylene glycol
Demand will be further increased.
Ethylene glycol process route is broadly divided into petroleum path and coal base route.In recent years, coal base route is quickly grown, and is passed through
Ji property also gradually steps up.For example, the production cost of the coal-ethylene glycol of Xinjiang production is at 2500-3000 yuan/ton, no matter from absolute
Profit margin still compared with the relative cost of other supply countries, there is certain competitiveness.
Coal ethyl glycol route mainly passes through CO gas-phase catalytic coupling legal system methyl oxalates and then hydrogenation synthesizing of ethylene glycol.Its
After the NO of middle coupling reaction generation separates with product, generation methyl nitrite and returning was coupled again with oxygen and methanol reaction
Journey recycles, i.e. methyl nitrite regenerative response：
4NO+O2+4CH3OH→4CH3ONO+2H2O (1)
This reaction is gas-liquid two-phase nitration reaction, and reaction speed is fast and thermal discharge is big.It is industrial at present to use filler bubbling bed more
Reacted, the low (200~2000m of gas liquid interfacial area-1), mass transfer ability is relatively low.Thus reactor apparatus volume is often larger
To increase the reaction time, the operational efficiency of reactor is relatively low.In addition, residence time of material grows (Li etc. in tower reactor
Ind.Eng.Chem.Res,2013,52:2814-2823), easily generate larger amount of nitric acid (2%~4% even more high,
CN201310416056), serious corrosion is produced to equipment.
The content of the invention
Present invention aims at provide a kind of method of microreactor synthesis methyl nitrite.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of method of microreactor synthesis methyl nitrite includes two steps of pre-reaction and micro- reaction, pre-reaction step
The mixed gas containing oxynitrides is generated, micro- reactions steps synthesize methyl nitrite.
The pre-reaction step uses tubular reactor, makes to include NO, O2、N2Mixed gas in the tubular reactor
Reaction generation contains N2、N2O3And NO2Gaseous mixture, reaction carry out at normal temperatures, gas residence time is in 1~15min；Or, reaction
In 80~120 DEG C of reactions, 1~2 second residence time；NO and O in tubular reactor inlet gas2Mol ratio be 4~7, preferably 4~
5, N2Volume content is 40~70%, preferably 50-55%.
Micro- reaction is carried out in single channel microreactor or multichannel microreactor, is made methanol and is contained oxynitrides
Mixed gas reaction generation methyl nitrite；In microreactor methanol and raw material NO mol ratios be 1~2, preferably 1.2~
1.5；Pressure limit is 0.1~0.5MPa, preferably 0.1~0.3MPa.
The microreactor, the hydraulic diameter of single channel and/or multichannel in micro- reaction channel are micro- for 100~3000
Rice, 10~100 centimetres of length, microreactor air speed is 2000~50000h-1, reaction temperature is 0~50 DEG C.
Microreactor outlet material is through gas-liquid separator separates gas phase and liquid phase.Exit Partial Liquid Phase material with it is fresh
Microreactor reaction is returned after methanol mixing.The fine grid of the optional band of gas-liquid separator type (20~30 microns of size) it is micro-
Type separator, gravity separator and cyclone separator, preferably cyclone separator.
Compared with prior art, the advantage of the invention is that：
1) gas-liquid mixed efficiency high, reaction is efficient, methanol usage amount low compared with prior art more than 30%.Short residence time makes
The growing amount of accessory substance nitric acid is greatly reduced.
2) heat-transfer capability is strong, and course of reaction is carried out at normal temperatures, and energy consumption is low.
3) reaction safety, N2Content is low (40%~70%), reduces reactor volume and kinetic equation loss.
4) parallel amplification and yardstick, which amplify, is used in combination, and production capacity amplification is simple.
Brief description of the drawings
Fig. 1 is methyl nitrite regenerative response technological principle schematic diagram.Wherein, 1- contains NO and N2Gaseous mixture, 2-O2, 3-
N2, 4- contains N2O3Gaseous mixture, 5- fresh methanols, 6- recovery methanol, 7- methanol charges, gas-liquid mixture after 8- reactions, 9- products
Gas, 1.-tubular type pre-reactor, 2.-microreactor, 3.-gas-liquid separator.
Embodiment
Mainly contain NO and N after coupling reaction and separation2Gaseous mixture 1 and O22 through tubular reactor 1. pre-reaction life
Into N2O3Gaseous mixture 4, separately have N23 are used to adjust gaseous mixture composition and blow device, and 1. exit gas enters tubular reactor
Microreactor is 2. interior to carry out esterification with methanol, generates methyl nitrite, NO/O in inlet gas2Molar ratio range is containing end
It is worth for 4~7, preferably 4~5；N2Volume content is 40~70% containing end value, preferably 50-55%, gas-liquid mixture after reaction
8 through 3.-gas-liquid separator, and the methanol for separating and recovering to obtain returns to microreactor after being mixed with fresh methanol 5 and 2. reacted.
Embodiment 1
In tubular reactor 1. entrance NO/O2Mol ratio is 4, gas phase N2Volume content 40%, pre-reaction temperature normal temperature, instead
Answer residence time 10min.2. 1000 microns of hydraulic diameter, gas phase air speed are 13000h to single channel microreactor-1, methanol/NO rubs
You are than being 2,50 DEG C of microreactor reaction temperature, and under system pressure condition of normal pressure, gaseous phase outlet methyl nitrite volume content is
43%, based on O2Product yield be 84.6%.
Embodiment 2
In tubular reactor 1. entrance NO/O2Mol ratio is 5, gas phase N2Volume content 60%, pre-reaction temperature normal temperature, instead
Answer residence time 8min.2. 300 microns of hydraulic diameter, gas phase air speed are 50000h to single channel microreactor-1, methanol/NO moles
Than for 2,30 DEG C of microreactor reaction temperature, under the conditions of system pressure is 0.2MPa, gaseous phase outlet methyl nitrite volume content
For 27.3%, based on O2Product yield be 85.3%.
Embodiment 3
In tubular reactor 1. entrance NO/O2Mol ratio is 4, gas phase N2Volume content 60%, 100 DEG C of pre-reaction temperature, reaction
Residence time 1.2s.2. 1000 microns of hydraulic diameter, gas phase air speed are parallel multi-channel (and number of lines 30) microreactor
50000h-1, gas phase N2Volume content 60%, NO/O2=4, methanol/NO mol ratios are 2,30 DEG C of microreactor reaction temperature, are
Pressure of uniting is under condition of normal pressure, and gaseous phase outlet methyl nitrite volume content is 31.6%, and the product yield based on oxygen is
80.2%.
Embodiment 4
In tubular reactor 1. entrance NO/O2Mol ratio is 4, gas phase N2Volume content 60%, 100 DEG C of pre-reaction temperature, reaction
Residence time 1.2s.2. 1000 microns of hydraulic diameter, gas phase air speed are parallel multi-channel (and number of lines 30) microreactor
50000h-1, gas phase N2Volume content 60%, NO/O2=4, methanol/NO mol ratios are 1.5,30 DEG C of microreactor reaction temperature,
System pressure is under condition of normal pressure, and gaseous phase outlet methyl nitrite volume content is 33%, and the product yield based on oxygen is
84.6%.
Claims (4)
- A kind of 1. method of microreactor synthesis methyl nitrite, it is characterised in that：Methods described includes pre-reaction and micro- reaction Two steps, mixed gas of the pre-reaction step generation containing oxynitrides, micro- reactions steps synthesize methyl nitrite.
- 2. the method that microreactor as claimed in claim 1 continuously synthesizes methyl nitrite, it is characterised in that：The pre-reaction step Suddenly tubular reactor is used, makes to include NO, O2、N2Mixed gas reacted in the tubular reactor generation contain N2、N2O3And NO2 Gaseous mixture, reaction carry out at normal temperatures, gas residence time is in 1~15min；Or, reaction is in 80~120 DEG C of reactions, stop 1~2 second time；NO and O in tubular reactor inlet gas2Mol ratio is 4~7, N2Volume content is 40~70%；Micro- reaction is carried out in single channel microreactor or multichannel microreactor, makes methanol and mixing containing oxynitrides Close gas reaction generation methyl nitrite；Methanol and raw material NO mol ratios are 1~2, preferably 1.2~1.5 in microreactor；Pressure Power scope is 0.1~0.5MPa, preferably 0.1~0.3MPa.
- 3. the method that microreactor as claimed in claim 2 continuously synthesizes methyl nitrite, it is characterised in that：The pipe reaction NO and O in device inlet gas2Mol ratio is 4~5, N2Volume content is 50-55%.
- 4. the method for continuous synthesis methyl nitrite as claimed in claim 2, it is characterised in that：The microreactor, micro- reaction The hydraulic diameter of single channel and/or multichannel in passage is 100~3000 microns, 10~100 centimetres of length, and microreactor is empty Speed is 2000~50000h-1, reaction temperature is 0~50 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109433144A (en) * | 2019-01-04 | 2019-03-08 | 山东豪迈化工技术有限公司 | Reaction unit, purposes and synthetic method in synthesis of methyl mercaptan sodium |
| CN110683955A (en) * | 2018-11-30 | 2020-01-14 | 中国科学院大连化学物理研究所 | Micro-reaction system and method for efficiently preparing methyl nitrite |
| CN113979867A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Nitric acid reduction equipment and method |
| CN114768700A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Nitric acid reduction device and method for reducing nitric acid |
| CN115124426A (en) * | 2022-03-31 | 2022-09-30 | 西安万德能源化学股份有限公司 | Environment-friendly continuous production process and system for isopropyl nitrate |
| CN116444399A (en) * | 2023-04-26 | 2023-07-18 | 济南大学 | Method for synthesizing (2E) -2-cyano-2-hydroxy iminoacetic acid ethyl ester by micro-reaction |
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| CN109433144A (en) * | 2019-01-04 | 2019-03-08 | 山东豪迈化工技术有限公司 | Reaction unit, purposes and synthetic method in synthesis of methyl mercaptan sodium |
| CN113979867A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Nitric acid reduction equipment and method |
| CN113979867B (en) * | 2020-07-27 | 2024-03-26 | 中国石油化工股份有限公司 | Nitric acid reduction equipment and method |
| CN114768700A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Nitric acid reduction device and method for reducing nitric acid |
| CN115124426A (en) * | 2022-03-31 | 2022-09-30 | 西安万德能源化学股份有限公司 | Environment-friendly continuous production process and system for isopropyl nitrate |
| CN116444399A (en) * | 2023-04-26 | 2023-07-18 | 济南大学 | Method for synthesizing (2E) -2-cyano-2-hydroxy iminoacetic acid ethyl ester by micro-reaction |
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