CN102311461A

CN102311461A - Method for preparing methyl cyclopentadienyl tricarbonyl manganese through continuous reaction

Info

Publication number: CN102311461A
Application number: CN2010102799504A
Authority: CN
Inventors: 刘江宁; 于万鹏; 晋平
Original assignee: HEBEI HUAGE FINE CHEMICAL CO Ltd
Current assignee: HEBEI HUAGE FINE CHEMICAL CO Ltd
Priority date: 2010-09-09
Filing date: 2010-09-09
Publication date: 2012-01-11

Abstract

The invention provides a method for preparing methyl cyclopentadienyl tricarbonyl manganese through continuous reaction. The method comprises the following steps of: (1) continuously adding methyl cyclopentadiene monomer and metal sodium into a reactor A in which a dehydration solvent is held; and (2) continuously feeding feed liquor into a reactor B from the reactor A, continuously adding anhydrous manganese chloride into the reactor B, and introducing CO gas into the reactor B to perform reaction. The method has the obvious advantages of full reaction, less byproducts, high yield and easiness in large-scale industrialization due to adoption of continuous reaction in an entire reaction process.

Description

A kind of successive reaction prepares the method for methyl cyclopentyl-dialkyl-tricarbon manganium

Technical field

The invention belongs to a kind of chemical products preparation method, particularly a kind of method for preparing methyl cyclopentyl-dialkyl-tricarbon manganium.

Technical background

Along with the increasingly stringent of developing of automobile industry and environmental requirement, methyl cyclopentyl-dialkyl-tricarbon manganium (being called for short MMT) receives people's favor day by day as the efficient additive of boosting of octane rating, has been the best substitute of tetraethyllead by generally acknowledging.Since the MMT appearance, the synthesis technique of methyl cyclopentyl-dialkyl-tricarbon manganium has been gone through four-stage: two step of (1) HTHP synthesis method; (2) two step of normal temperature and pressure synthesis method; (3) improve two step of HTHP synthesis method; (4) HTHP one-step synthesis.People constantly improve its synthesis technique, disclose number of patents, like USP 2818417, USP2839552; USP 3127351, and USP 5026885, and USP 4946975; USP 2916504, ZL99121176.6, CN 101024656A etc.; These patented technologies all have a common trait, that is: methyl cyclopentadiene or sodium Metal 99.5 join in the reaction vessel off and on, carry out rhythmic reaction; Manganese chloride anhydrous joins in the reaction vessel off and on, and logical then CO carries out rhythmic reaction.There are many defectives in this kind rhythmic reaction mode, as react insufficient, by product is many, inconvenient operation, yield and quality instability etc. between batch.

Summary of the invention

The technical issues that need to address of the present invention are, overcome the above-mentioned deficiency of prior art, provide a kind of successive reaction to prepare the method for methyl cyclopentyl-dialkyl-tricarbon manganium; Its sufficient reacting, by product is few, and yield is high; Convenient operation and control, and be easy to large-scale continuous production.

Method of the present invention comprises the steps:

(1) in reactor A, pack into the dehydration after solvent, be replaced into inert atmosphere, successive is to wherein adding methyl cyclopentadiene monomer and sodium Metal 99.5 then;

(2) reaction solution gets into from the reactor A successive and has been replaced into the reactor B of inert atmosphere, and the Manganese chloride anhydrous successive joins in the reactor B, and reacts to wherein feeding CO gas.

Above-mentioned solvent be not with the organic ether compounds or the aromatic hydrocarbon solvent of sodium Metal 99.5 reaction, be preferably: 1,4-dioxane, THF, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, morpholine, benzene, toluene, ethylbenzene, YLENE etc.

In reactor A, add the solvent after the dehydration, and add methyl cyclopentadiene and sodium Metal 99.5 to successive wherein, keeping temperature is 130～350 ℃, and the mean residence time of material in reactor A is 0.5～4h; The feed liquid successive gets into the reactor B from reactor A; The Manganese chloride anhydrous successive joins among the reaction B, feeds CO to reactor B and reacts, and keeps CO pressure 3～15MPa; Keep 50～350 ℃ of temperature, the mean residence time of feed liquid in reactor B is 0.5～10h.

Above-mentioned reactor A adopts shell-and-tube reactor, continuous flow tank reactor or annular-pipe reactor form; Reactor B adopts bubbling stirring tank or fluidized-bed reactor form.

The present invention and existing preparation methyl cyclopentyl-dialkyl-tricarbon manganium compared with techniques; Have very significant advantage: (1) methyl cyclopentadiene monomer and sodium successive join in the reactor A, and temperature of reaction is at 130～350 ℃, and sodium Metal 99.5 is liquid at this moment; Can know by the chemical reaction engineering ultimate principle; Successive reaction can make reaction more abundant than intermittent feeding, and yield is high, and by product is few; (2) feed liquid in the reactor A and Manganese chloride anhydrous successive join in the reactor B, in like manner can know, the reactive mode of this continuously feeding can make reaction more abundant, and yield is high, and by product is few; (3) the present invention has widened the use range of reaction solvent, and feasible reaction can carry out in the solvent cheaply, is beneficial to reduce production costs; (4) owing to adopted the successive reaction form, be easy to realize large-scale continuous production, and quality product is more stable.

Description of drawings

Fig. 1 is a schema of the present invention.

Embodiment

Visible by Fig. 1, method of the present invention comprises the steps:

(1) in reactor A, pack into the dehydration after solvent, be replaced into inert atmosphere, successive reacts to wherein adding methyl cyclopentadiene monomer and sodium Metal 99.5; (2) reaction solution gets into from the reactor A successive and has been replaced into the reactor B of inert atmosphere, and the Manganese chloride anhydrous successive joins in the reactor B, and reacts to wherein feeding CO gas.

Through several preferred examples of the present invention, particular content of the present invention is elaborated below.

Embodiment 1

In the continuous flow tank reactor of 1L, add 1,4-dioxane 400mL is replaced into nitrogen atmosphere, and sodium Metal 99.5 20g, methyl cyclopentadiene monomer 100mL time spent 1h successive are added in the still, keeps 150 ℃ of temperature of reaction; Material successive in the continuous flow still is imported in the bubbling stirring tank of 1L, Manganese chloride anhydrous 24g time spent 1h successive is joined in the bubbling stirring tank, and logical CO reacts 6h, keeping temperature is 70 ℃, and pressure is 5MPa.Remove solvent after reaction finishes, carry out rectifying, obtain the product methyl cyclopentyl-dialkyl-tricarbon manganium, product yield counts 86% with Manganous chloride tetrahydrate.

Embodiment 2

In shell-and-tube reactor, feed THF continuously, simultaneously sodium Metal 99.5 40g, methyl cyclopentadiene monomer 180mL time spent 3h successive are fed shell-and-tube reactor, keep 200 ℃ of temperature of reaction; Reacted material is imported in the bubbling stirring tank of 1L, Manganese chloride anhydrous 90g time spent 2h successive is joined in the bubbling stirring tank, and logical CO reacts 2h, keeping temperature is 110 ℃, and pressure is 9MPa.Remove solvent after reaction finishes, carry out rectifying, obtain the product methyl cyclopentyl-dialkyl-tricarbon manganium, product yield counts 85% with Manganous chloride tetrahydrate.

Claims

1. a successive reaction prepares the method for methyl cyclopentyl-dialkyl-tricarbon manganium; It is characterized in that it comprise the steps: (1) in reactor A, pack into the dehydration after solvent; Be replaced into inert atmosphere, successive is to wherein adding methyl cyclopentadiene monomer and sodium Metal 99.5 then; (2) reaction solution gets into from the reactor A successive and has been replaced into the reactor B of inert atmosphere, and the Manganese chloride anhydrous successive joins in the reactor B, and reacts to wherein feeding CO gas.

2. a kind of successive reaction as claimed in claim 1 prepares the method for methyl cyclopentyl-dialkyl-tricarbon manganium; It is characterized in that: wherein said solvent for not with the organic ether compounds or the aromatic hydrocarbon solvent of sodium Metal 99.5 reaction; Be preferably: 1,4-dioxane, THF, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, morpholine, benzene, toluene, ethylbenzene, YLENE.

3. according to claim 1 or claim 2 a kind of successive reaction prepares the method for methyl cyclopentyl-dialkyl-tricarbon manganium; It is characterized in that: in reactor A, add the solvent after dewatering; And add methyl cyclopentadiene and sodium Metal 99.5 to successive wherein; Keeping temperature is 130～350 ℃, and the mean residence time of material in reactor A is 0.5～4h; The feed liquid successive gets into the reactor B from reactor A; The Manganese chloride anhydrous successive joins among the reaction B, feeds CO to reactor B and reacts, and keeps CO pressure 3～15MPa; Keep 50～350 ℃ of temperature, the mean residence time of feed liquid in reactor B is 0.5～10h.

4. prepare the method for methyl cyclopentyl-dialkyl-tricarbon manganium like right 1 or 2 or 3 described a kind of successive reactions, it is characterized in that: described reactor A adopts shell-and-tube reactor, continuous flow tank reactor or annular-pipe reactor form; Reactor B adopts bubbling stirring tank or fluidized-bed reactor form.