CN101205168B - method for preparing methyl cyclopentadiene - Google Patents
method for preparing methyl cyclopentadiene Download PDFInfo
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- CN101205168B CN101205168B CN2007101150241A CN200710115024A CN101205168B CN 101205168 B CN101205168 B CN 101205168B CN 2007101150241 A CN2007101150241 A CN 2007101150241A CN 200710115024 A CN200710115024 A CN 200710115024A CN 101205168 B CN101205168 B CN 101205168B
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Abstract
The invention relates to a method for preparing a methyl cyclopentadiene in the field of the preparation method for fine chemical products. The liquefied methane chloride in a storage tank is directly added into a reactor without being gasified so as to go through a liquid phase reaction with the cyclopentadienyl sodium or cyclopentadienyl potassium. The more accurate measurement is carried out in the process of the addition of the liquefied methane chloride. and the liquefied methane chloride is led in from the bottom of the reactor. In order to adapt to the homogeneous reaction, the methylation reaction of the invention is undergone under the hermetic condition, the pressure in the reactor ranges from 0 to 0.5MPa (gauge pressure) and the reaction temperature ranges from -10 DEG C to 40 DEG C. The invention has the advantages that gas-liquid heterogeneous reaction is converted into the liquid phase reaction, the invention intensifies the concentration of the methylane chloride in the reaction solution, enhances the reaction velocity and conversion rate, and solves the problem of the measurement of the methane chloride so as to smooth the implementation of the reaction.
Description
Technical field
The present invention relates to a kind of method for preparing methyl cyclopentadiene in the fine chemical product preparation method field.
Technical background:
Methyl cyclopentadiene, the chemical abstracts name is called: 1,3-cyclopenta-diene methyl, English name: Methylcyclopentadiene abbreviates as: MCPD, be a kind of basic chemical raw materials, its outward appearance is rendered as a kind of colourless liquid, 71 ℃ of boiling points, fusing point-51 ℃ (95%), be soluble in ethanol, ether and benzene, water insoluble.The chemical structural formula of this material such as figure below.
Methyl cyclopentadiene exists with dimeric form usually, and dimeric boiling point is 200 ℃.
Methyl cyclopentadiene is as a kind of broad-spectrum basic chemical raw materials, mainly as various metal derivatives, polymer agent, fire retardant etc.As the methyl cyclopentadienyl tricarbonyl manganese (MMT) with the MCPD preparation is a kind of gasoline knock-compound, has energy-conservation, minimizing pollution characteristics; And for example be used for preparing epoxy curing agent methyl carbic anhydride (MNA), owing to there is methyl to exist in its molecule, its chemical products has more superior character and purposes than cyclopentadiene on some performance.But the direct sources of methyl cyclopentadiene is limited, is the important channel with cyclopentadiene in order to the preparation methyl cyclopentadiene.And cyclopentadiene is C in the cracking production ethylene process
5One of by product in the cut.Since the eighties, the development of China ethylene production is very fast, to nineteen ninety throughput reached 208.7 ten thousand tons.C
5Cut normally ethylene yield 14～17%, wherein cyclopentadiene accounts for 16%, by this estimation China cyclopentadiene can be arranged more than 50,000 tons every year.C
5Only about 20%, remaining acts as a fuel and burns in the development and use of cut, and a large amount of cyclopentadiene waits development and use, and preparing methyl cyclopentadiene with cyclopentadiene is the approach that well utilizes.
At present industrial mainly is to be that alkali reactions such as raw material and sodium Metal 99.5, potassium or sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood generate cyclopentadiene sodium or cyclopentadiene potassium with the cyclopentadiene, carries out methylation reaction with monochloro methane again and produces methyl cyclopentadiene.As seen producing methyl cyclopentadiene is finished by two-step reaction: the first step is to produce cyclopentadiene sodium or cyclopentadiene potassium, second step was to carry out methylation reaction to obtain methyl cyclopentadiene, this two-step reaction both can be finished in same reactor, also can in a reactor, carry out the first step reaction, material be poured into carried out the reaction of second step in another reactor then.The patent of invention of Dongchang fine chemistry industry Science and Technology Ltd. " is produced cyclopentadiene sodium technology " (ZL03138766.7, the applying date: on July 9th, 2003, Granted publication day: on June 22nd, 2005), the first step of above-mentioned reaction is disclosed.For the research and development of subsequent technology is laid a good foundation.
Existing methylation reaction is that the cyclopentadiene sodium solution that monochloro methane gas (the monochloro methane fusing point :-97.7 ℃, boiling point :-24 ℃, normal temperature is down gas phase) feeds in the reactor with liquid phase is carried out methylation reaction, and its reaction equation is as follows:
Monochloro methane is participated in reaction in the gas mode, be the solution-air inhomogeneous reaction, this is disadvantageous to methylation reaction, because: gas-liquid reaction influences the mass transfer process of monochloro methane and cyclopentadiene sodium, monochloro methane is dissolved in by gas phase in the cyclopentadiene sodium solution of liquid phase could participate in reaction, carrying out along with reaction, monochloro methane in the solution constantly is consumed, monochloro methane in the gas phase constantly replenishes into, but the monochloro methane in the solution maintains under the lower concentration all the time, reduce speed of response, prolonged the reaction times.And this methylation reaction is a strong exothermal reaction, to temperature of reaction system is raise, reaction heat must be taken away, and to keep lower temperature of reaction, temperature of reaction system raises, and can further reduce the solubleness of monochloro methane, reduces speed of response.Monochloro methane normally is stored in the basin with liquid form, add reaction system in the gas mode, must gasify to monochloro methane, to absorb a large amount of heats in the gasification, reduce ambient temperature, have refrigeration, and this part cold is difficult to reclaim, cause waste, particularly more considerable in industrial production.Monochloro methane adds reaction system in the gas mode, is not easy to the metering of reaction mass, and methylation reaction is also caused disadvantageous effect, because the monochloro methane add-on is crossed reaction at least not exclusively, reduce yield, the monochloro methane add-on is too much, and the probability that side reaction then occurs wants big.
Summary of the invention:
The objective of the invention is that there is the deficiency of above-mentioned reaction in method at the monochloro methane gas-phase feed and a kind of method for preparing methyl cyclopentadiene of proposing.It is the improvement of carrying out on existing method, to improve its reaction efficiency.
The present invention adopts the method for monochloro methane liquid phase feeding, the liquid monochloro methane in the basin is directly added in liquid mode without gasification carry out liquid phase reaction in the reactor.The said reactor of the present invention is the common reactor that has charging, discharge port, has whipping appts etc.In order effectively to control the adding quantity of monochloro methane, can add a test tank liquid towards monochloro methane before monochloro methane enters reactor measures more accurately, also can install under meter additional on monochloro methane enters the pipeline of reactor measures, said flow is counted suitable liquid flow measurement general in the chemical field, and is suitable for the under meter of this material.For liquid monochloro methane better is dissolved in the liquid phase material, liquid monochloro methane is fed by reactor bottom.In order to adapt to this homogeneous reaction, methylation reaction of the present invention carries out under air-tight state, and pressure is 0 to 0.5MPa (gauge pressure) in the reactor, and temperature of reaction is-10 ℃ to 40 ℃.
Advantage of the present invention is: become the solution-air inhomogeneous reaction and be liquid phase reaction, improved the concentration of monochloro methane in reaction soln, improved speed of response and transformation efficiency; And solved the monochloro methane measurement problem, helped reaction and carry out.
Embodiment
Following example describes the principle of the invention, but the invention is not restricted to following example.
Liquid monochloro methane is pressed into the test tank of band liquid level emasuring device by basin, be pressed in the reactor by reactor bottom (or bottom) by desired number again, react, other reaction mass is added prior to monochloro methane by the reactor upper entrance, the amount of each material and proportioning in the reaction should consider that the stoichiometric coefficient of reaction equation, the needs that suppress side reaction, the factors such as cost of material determine.The monochloro methane add-on is 400 liters in this example, and reaction solution is 3000 liters, and the mol ratio of cyclopentadiene sodium and monochloro methane is 1: 1.2.Reaction pressure 0.1MPa (gauge pressure), in 8 hours reaction times, the methylation reaction transformation efficiency is 95% (in cyclopentadiene sodium).And monochloro methane adds in the reactor with the gas phase form, reaches same transformation efficiency, and the reaction times is wanted 40 to 50 hours.
Claims (6)
1. method for preparing methyl cyclopentadiene, be to be that raw material reacts generation cyclopentadiene sodium or cyclopentadiene potassium with comprising sodium Metal 99.5, potassium or sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood with the cyclopentadiene, carry out methylation reaction with monochloro methane again and produce methyl cyclopentadiene, it is characterized in that: monochloro methane adds with liquid form participates in reaction in the reactor.
2. the method for preparing methyl cyclopentadiene as claimed in claim 1 is characterized in that: liquid monochloro methane adopts test tank to measure.
3. the method for preparing methyl cyclopentadiene as claimed in claim 1 is characterized in that: liquid monochloro methane adopts under meter to measure.
4. the method for preparing methyl cyclopentadiene as claimed in claim 1 is characterized in that: liquid monochloro methane enters reactor by reactor lower part or bottom.
5. the method for preparing methyl cyclopentadiene as claimed in claim 1 is characterized in that: methylation reaction is a kind of confined reaction, and reaction pressure is 0 to 0.5Mpa by gauge pressure.
6. the method for preparing methyl cyclopentadiene as claimed in claim 1 is characterized in that: the methylation reaction temperature is-10 ℃ to 40 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101150241A CN101205168B (en) | 2007-11-22 | 2007-11-22 | method for preparing methyl cyclopentadiene |
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| CN2007101150241A CN101205168B (en) | 2007-11-22 | 2007-11-22 | method for preparing methyl cyclopentadiene |
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| CN101205168A CN101205168A (en) | 2008-06-25 |
| CN101205168B true CN101205168B (en) | 2011-12-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617531B (en) * | 2012-03-12 | 2014-04-16 | 濮阳惠成电子材料股份有限公司 | Method for using mixed C5 to produce methyl nadic anhydride |
| CN103641676A (en) * | 2013-11-01 | 2014-03-19 | 江西西林科股份有限公司 | Method for preparing methyl cyclopentadiene |
| CN111569947A (en) * | 2020-06-19 | 2020-08-25 | 安徽国星生物化学有限公司 | Method for synthesizing 2-methylpyridine organic cobalt catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547603A (en) * | 1982-04-23 | 1985-10-15 | Ethyl Corporation | Methylcyclopentadiene synthesis |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547603A (en) * | 1982-04-23 | 1985-10-15 | Ethyl Corporation | Methylcyclopentadiene synthesis |
Non-Patent Citations (2)
| Title |
|---|
| 李琦斌.环戊二烯合成甲基环戊二烯.《石油化工》.2007,第36卷(第6期), * |
| 胡石金.甲基化反应合成甲基环戊二烯的研究.《南昌工程学院学报》.2006,第25卷(第3期),第66页1.3. * |
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