CN106543026B - A kind of preparation method of methyl hydrazine - Google Patents
A kind of preparation method of methyl hydrazine Download PDFInfo
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- CN106543026B CN106543026B CN201610929564.2A CN201610929564A CN106543026B CN 106543026 B CN106543026 B CN 106543026B CN 201610929564 A CN201610929564 A CN 201610929564A CN 106543026 B CN106543026 B CN 106543026B
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- hydrazine
- methanol
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- methyl hydrazine
- hydrazine hydrate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
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Abstract
The invention discloses a kind of method that one-step method prepares methyl hydrazine; this method is under inert gas shielding; hydrazine hydrate and methanol are alkylated reaction one-step synthesis methyl hydrazine under catalyst action; keep methanol excessive during the course of the reaction, the mixed liquor reacted after terminating is obtained into the methyl hydrazine solution of high-purity by rectifying.The invention has the advantages that：Process route is short, simple to operate, and reaction yield is high；Catalyst choice is high, and reaction condition is gentle, and side reaction and accessory substance are few；Catalyst and unreacted methanol, hydrazine hydrate are circularly used for alkylated reaction, and without using solvent, three wastes produce, green.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of preparation method of methyl hydrazine.
Background technology
Methyl hydrazine is a kind of important energy and material, meanwhile, and some high-quality agricultural chemicals of synthesis, the important centre of medicine
Body.It is many for the preparation method report of methyl hydrazine, mainly there are following several preparation methods according to existing literature：
Chloramine method：Patent US4192819 discloses the technique of chloramine method synthesizing methyl hydrazine earliest, mainly using sodium hypochlorite
Production chloramines is reacted with ammonia, then by chloramines and monomethyl amine reaction generation methyl hydrazine.Technique is ripe, but the route is follow-up
Separating difficulty is big, production process high energy consumption, equipment cost are big.
Hydrazine hydrate benzaldehyde method：Using hydrazine hydrate as raw material and benzaldehyde reaction generation benzal azine, then add sulfuric acid two
Methyl esters generates methylhydrazinium sulphate, through in caustic alcohol and rectifying.Product yield 60% ~ 70%.But whole reaction raw materials cost compared with
Height, course of reaction is more complicated, energy consumption is larger, smell is larger in production process, is unfavorable for industrialized production.
Dimethylphosphite or dimethyl carbonate hydrazine hydrate method：Methylated examination with dimethylphosphite or dimethyl carbonate
Agent, the optimum reaction condition with hydrazine hydrate direct synthesizing methyl hydrazine in atmospheric conditions, the according to the literature synthesis of this technique, a first
The reaction yield of base is 50%, but same selected methylating reagent price is higher, and reaction yield is comparatively relatively low.
One hydrazinoethanol decomposition method：Decomposed by the thermodynamics of 2-hydrazinoethanol to prepare monomethyl hydrazine, be prepared by one kind
The new method of monomethyl hydrazine, 2-hydrazinoethanol is positioned in reactor, is heated to 200 ~ 225 DEG C, makes its decomposition, liquid point
Solution product is further evaporated under reduced pressure separation and obtains the azeotropic mixture of water and methyl hydrazine, then takes with desiccant dryness such as NaOH, enters one
Air-distillation is walked to obtain methyl hydrazine.The technological advantage is that reaction is simple, and purification is easier to.Shortcoming is that hydrazinoethanol decomposes easily production
Raw to split quick-fried, reaction is unstable, and production process has serious potential safety hazard.
N- nitro methylamine hydrogenation methods：N- nitro methylamines are raw by hydrogenation reduction in the case where making catalyst with palladium
Into mixture in, monomethyl hydrazine can be by adding appropriate acid to form acid hydrazine, and separated goes out the monomethyl hydrazine aqueous solution, root
According to needing to carry out purification concentration again.The method advantage is that raw material is easy to get, and production cost is low.Shortcoming is to need high pressure, and palladium is urged
Agent cost is higher, is adapted to small-scale experiment production, is unfavorable for large-scale industrial production.
Dimethyl suflfate hydrazine hydrate method：Patent CN101402586A discloses one kind by hydrazine hydrate and dimethyl suflfate with salt
Acid is used as protective agent, and TBAB generates methylhydrazinium sulphate as catalyst at 115 ~ 125 DEG C, then in highly basic hydrogen
Pass through the isolated required methyl hydrazine solution of rectifying under sodium oxide molybdena the condition of dissociation.This method raw material is easy to get, is cheap, be anti-
The advantages that answering fast speed, high income.But dimethyl suflfate toxicity is larger to have potential safety hazard, while can be remained after free end
A large amount of intractable sodium salts, this undoubtedly adds sodium salt processing cost and brings cumbersome environmental issue, therefore this set
Technique is difficult to carry out industrialized production.
Hydrazine hydrochloride methanol method：Patent CN102516117B is disclosed one kind and reacted under high pressure with hydrazine hydrochloride and methanol, then
Dissociated methyl hydrazine hydrochloride with hydrazine hydrate, then the method for producing methyl hydrazine by distillation and rectification process.This method step is more, instead
Answer pressure high, equipment investment is big, can produce more accessory substance 1,2- dimethylhydrazines.
Monochloro methane hydrazine hydrate method：Patent CN105037196A discloses a kind of side of catalytic synthesis of methyl hydrazine under normal pressure
Method.It is characterized in that：Hydrazine hydrate and monochloro methane are made into protective agent with hydrochloric acid, silica gel makees catalyst, ethanol as solvent, 70 ~ 74 DEG C
Lower synthesis under normal pressure, methyl hydrazine hydrochloride is generated, then dissociated methyl hydrazine with hydrazine hydrate, it is water-soluble to obtain methyl hydrazine through rectification process
Liquid.This method reactions steps are more, need recycling design and catalyst, high energy consumption, and hydrochloric acid has requirement of the corrosivity to equipment high.
The content of the invention
In order to overcome disadvantages mentioned above existing for prior art, the invention provides a kind of process route is short, accessory substance is few, receive
Rate is high, the prices of raw materials are cheap, energy-conserving and environment-protective, the methyl hydrazine novel preparation method of economic security.
The technical solution adopted by the present invention is：Following steps are carried out under inert gas shielding：
1st, methanol and hydrazine hydrate are put into reactor, catalyst sodium hydrogensulfite are then added into reactor and to first
Benzene sulfonic acid sodium salt, closed reactor, it is warming up to 70-100 DEG C and is alkylated reaction, the reaction time is 3-5 hours, is contained
The mixed liquor of methyl hydrazine.During the course of the reaction, methanol should be kept excessive, the mol ratio of methanol and hydrazine hydrate is 1-2: 1, sulfurous acid
The addition of hydrogen sodium and paratoluenesulfonic acid sodium salt is respectively 5%-the 30% of hydrazine hydrate quality, and its reaction equation is as follows：
CH3OH + NH2NH2·H2O —→ CH3NHNH2 + 2H2O
2nd, it is transferred to after the methyl hydrazine mixed liquor that step 1 obtains being cooled into 60 DEG C in rectifying still, is to slowly warm up to seethe with excitement,
The methanol steamed is collected at 65-70 DEG C of temperature, is continuously heating to 90-100 DEG C, the methyl hydrazine steamed is collected, after rectifying terminates
By bottoms（Sodium hydrogensulfite, p-methyl benzenesulfonic acid sodium catalyst and unreacted hydrazine hydrate）Step 1 is transferred to the methanol steamed
Reactor in be used for alkylated reaction.
The present invention is under inert gas shielding, and hydrazine hydrate and methanol are alkylated into reaction one under catalyst action
Synthesizing methyl hydrazine is walked, keeps methanol excessive during the course of the reaction, the mixed liquor reacted after terminating is obtained into high-purity by rectifying
Methyl hydrazine solution, while reclaim unreacted methanol, hydrazine hydrate and catalyst, they are continued on for into alkylated reaction produces
Methyl hydrazine.Compared with prior art, the beneficial effects of the invention are as follows：（1）Course of reaction is simple, and process route is short, reaction yield
Height, reach more than 95% with hydrazine hydrate rate of collecting；（2）Catalyst choice is high, and the growing amount of more alkylate by-products is few；（3）
Catalyst and unreacted methanol, hydrazine hydrate are recycled for alkylated reaction, and without using solvent, three wastes produce, green ring
Protect；（4）Being alkylated reaction with free hydrazine replacement hydrazonium salt reduces reaction temperature, reduces the hair of decomposition and the side reaction of hydrazine
It is raw, save energy consumption.
Embodiment
Percentage composition as described below is mass fraction, and the yield of methyl hydrazine is with the consumption gauge of hydrazine hydrate, all steps
Completed under inert gas shielding.
Embodiment 1
The hydrazine hydrate that 360g methanol and 625g concentration are 80% is put into reactor, then by 53g sodium hydrogensulfites and
82g paratoluenesulfonic acid sodium salts are added in reactor, closed reactor, open stirring, are warming up to 86 DEG C, will be anti-after reacting 5 hours
Answer liquid temperature degree to drop to 60 DEG C, reaction solution is transferred in rectifying still and is warming up to 65-70 DEG C, steam methanol 87g, be continuously heating to
90-110 DEG C, steam methyl hydrazine 393g.Rectifying terminates to contain hydrazine hydrate 55g in rear bottoms, and methyl hydrazine yield is 96.1%.
Embodiment 2
The methanol 87g that rectifying in embodiment 1 is reclaimed and the bottoms containing hydrazine hydrate 55g are transferred in reactor, are supplemented
33g sodium hydrogensulfites and 25g paratoluenesulfonic acid sodium salts, are then added to instead by 393g methanol and the hydrazine hydrate that 742g concentration is 60%
Answer in kettle, closed reactor, open stirring, be warming up to 98 DEG C, reacting liquid temperature is dropped to 60 DEG C after reacting 3 hours, will be reacted
Liquid, which is transferred in rectifying still, is warming up to 65-70 DEG C, steams methanol 196g, is continuously heating to 90-110 DEG C, steams methyl hydrazine 405g.
Rectifying terminates to contain hydrazine hydrate 48g in rear bottoms, and methyl hydrazine yield is 97.3%.
Embodiment 3
The methanol 196g that rectifying in embodiment 2 is reclaimed and the bottoms containing hydrazine hydrate 48g are transferred in reactor, are mended
284g methanol and 753g concentration are filled for 60% hydrazine hydrate, closed reactor, are opened stirring, are warming up to 95 DEG C, after reacting 3 hours
Reacting liquid temperature is dropped to 60 DEG C, reaction solution is transferred in rectifying still and is warming up to 65-70 DEG C, steams methanol 200g, continues to heat up
To 90-110 DEG C, methyl hydrazine 399g is steamed.Rectifying terminates to contain hydrazine hydrate 52g in rear bottoms, and methyl hydrazine yield is 96.9%.
Embodiment 4
The methanol 200g that rectifying in embodiment 3 is reclaimed and the bottoms containing hydrazine hydrate 52g are transferred in reactor, are mended
376g methanol and 1120g concentration are filled for 40% hydrazine hydrate, are then added to 45g sodium hydrogensulfites and 39g paratoluenesulfonic acid sodium salts
In reactor, closed reactor, stirring is opened, be warming up to 75 DEG C, reacting liquid temperature is dropped to 60 DEG C after reacting 4 hours, will be anti-
Answer liquid to be transferred in rectifying still and be warming up to 65-70 DEG C, steam methanol 285g, be continuously heating to 90-110 DEG C, steam methyl hydrazine
414g.Rectifying terminates to contain hydrazine hydrate 42g in rear bottoms, and methyl hydrazine yield is 98.2%.
Claims (1)
- A kind of 1. preparation method of methyl hydrazine, it is characterised in that：Following steps are carried out under inert gas shielding：（1）Methanol and hydrazine hydrate are put into reactor, the mol ratio of methanol and hydrazine hydrate is 1-2: 1, then into reactor The addition of addition catalyst sodium hydrogensulfite and paratoluenesulfonic acid sodium salt, sodium hydrogensulfite and paratoluenesulfonic acid sodium salt is respectively hydrazine hydrate 5%-the 30% of quality；（2）Closed reactor, stirring to be opened, be warming up to 70-100 DEG C and be alkylated reaction, the reaction time is 3-5 hours, Reaction obtains the mixed liquor containing methyl hydrazine after terminating；（3）By step（2）In the mixed liquor containing methyl hydrazine be cooled to 60 DEG C after be transferred in rectifying still, be to slowly warm up to seethe with excitement, The methanol steamed is collected at 65-70 DEG C of temperature, 90-100 DEG C is continuously heating to, collects the methyl hydrazine steamed, rectifying terminates Bottoms and the methanol steamed are transferred in reactor and continue on for alkylated reaction afterwards.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503418B (en) * | 2018-12-11 | 2021-06-08 | 河北合佳医药科技集团股份有限公司 | Preparation process of methylhydrazine |
| CN111320554A (en) * | 2019-12-11 | 2020-06-23 | 东力（南通）化工有限公司 | Improved technology of monomethylhydrazine production process |
| CN114292208B (en) * | 2021-12-27 | 2023-11-28 | 杭州新本立医药有限公司 | Method for preparing methyl hydrazine by solid acid catalysis |
| CN115232023B (en) * | 2022-06-23 | 2023-08-04 | 东力（南通）化工有限公司 | Process for catalytic synthesis of methyl hydrazine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855501A (en) * | 1980-12-10 | 1989-08-08 | Japan Hydrazine Co., Inc. | Process for preparation of monomethylhydrazine |
| CN101260067A (en) * | 2007-03-07 | 2008-09-10 | 抚顺市化工研究设计院 | Mono-methylation method for hydrazine |
| CN102516117A (en) * | 2011-12-06 | 2012-06-27 | 东力（南通）化工有限公司 | Process for producing methyl hydrazine with hydrazine hydrate method |
| CN105037196A (en) * | 2015-08-10 | 2015-11-11 | 济南大学 | Novel method of catalytic synthesis of methylhydrazine under normal pressure |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0239502B2 (en) * | 1982-03-15 | 1990-09-05 | Nippon Hydrogene Kogyo | MONOMECHIRUHIDORAJINNOKAISHUHOHO |
| JPS60237059A (en) * | 1984-05-09 | 1985-11-25 | Nippon Carbide Ind Co Ltd | Preparation of monoalkylhydrazine |
-
2016
- 2016-10-31 CN CN201610929564.2A patent/CN106543026B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855501A (en) * | 1980-12-10 | 1989-08-08 | Japan Hydrazine Co., Inc. | Process for preparation of monomethylhydrazine |
| CN101260067A (en) * | 2007-03-07 | 2008-09-10 | 抚顺市化工研究设计院 | Mono-methylation method for hydrazine |
| CN102516117A (en) * | 2011-12-06 | 2012-06-27 | 东力（南通）化工有限公司 | Process for producing methyl hydrazine with hydrazine hydrate method |
| CN105037196A (en) * | 2015-08-10 | 2015-11-11 | 济南大学 | Novel method of catalytic synthesis of methylhydrazine under normal pressure |
Non-Patent Citations (2)
| Title |
|---|
| Kinetics of catalytic hydrogenation of methoxy-NNO-azoxymethane and Bis(methoxy-NNO-azoxy)methane;I. N. Zyuzin et al.;《Russian Journal of General Chemistry》;20121231;第82卷(第11期);第1891-1893页 * |
| Synthesis of methylhydrazine and 1,1-dimethylhydrazine by the reactions of hydroxylamine-O-sulfonic acid with methyl- and dimethylamine;Harry H. Sisler et al.;《Inorg. Chem.》;19801231;第19卷;第2846-2848页 * |
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Effective date of registration: 20171220 Address after: 051530, Shijiazhuang, Hebei province Zhaoxian County new walled shop Industrial Park Applicant after: Shijiazhuang Jinpai Pharmaceutical Chemical Co. Ltd. Address before: 408099 Chongqing city Fuling District Daoxiang Road No. 40 9-17 Applicant before: CHONGQING JINSHAN SCIENCE & TECHNOLOGY CO., LTD. |
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