CN104084102A - Method for realizing anhydrous anaerobic operation and ring manganese reaction production process of methyl cyclopentadienyl manganese by method - Google Patents
Method for realizing anhydrous anaerobic operation and ring manganese reaction production process of methyl cyclopentadienyl manganese by method Download PDFInfo
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Abstract
The invention relates to a method for realizing anhydrous anaerobic operation and a ring manganese reaction production process of methyl cyclopentadienyl manganese by the method. The method comprises the following steps: (1) arranging a micro-positive pressure breather valve on a venting pipeline of a reaction still, and injecting inert gas to keep the micro-positive pressure state in the reaction still before feeding, wherein the gauge pressure of the micro-positive pressure is not greater than 400 Kpa; and (2) filling the reaction still with micro-flow inert gas through a small-range flowmeter, and opening a charging hole for charging, wherein inert gas always flows out of the still, and the flow of inert gas is controlled within 20-200 L/minute. According to the method, the reaction still is capable of using inert gas as less as possible and completing material charging and discharging under the protection of inert gas, so that the risk of reaction failure is decreased.
Description
Technical field
The present invention relates to fine chemistry industry production field, say more specifically a kind of ring manganese reaction production technology that realizes the method for anhydrous and oxygen-free operation and the methyl cyclopentadienyl manganese of application the method.
Background technology
In some materials of many materials, particularly mankind's synthesized, have much air-sensitive, unstable to airborne oxygen and moisture, such as alkali metal, organic alkali metal, free radical, anaerobic organism, cyclopentadienyl group manganese, methyl cyclopentadienyl manganese etc.Therefore, if research and produce in while relating to these compounds, such as producing MMT(: methyl cyclopentyl-dialkyl-tricarbon manganium) and CMT(: cyclopentadiene tricarbonyl manganese) time, all need under anhydrous and oxygen-free condition, operate.
Ensure in the water-free situation of reaction mass, in laboratory, anhydrous and oxygen-free operating technology adopts 3 kinds of methods at present: 1.Schlenk operating technology repeatedly vacuumizes with filling with inert gas and realize with Schlenk type glass apparatus; 2. high vacuum line operating technology (vacuum-line) is in unorganic glass pipe or in metal instrumentation and use liquid nitrogen cold trap, is evacuated to 10 with oil-sealed rotary pump
-7~ 10
-4the high vacuum of KPa; 3. in the glove box that glove box operating technology (glove-box) is made with lucite, pass into and put into drier after inert gas replacement air wherein and realize.Every kind of method has limitation separately and suitable application above.In suitability for industrialized production, general employing repeatedly vacuumizes with filling with inert gas and replaces to realize anhydrous and oxygen-free operation, similar with Schlenk operating technology.
In the suitability for industrialized production of the types such as the cultivation of the bacterial classification of the macromolecule of organometallic synthetic, radical polymerization, anaerobism, the operating condition of anhydrous and oxygen-free is related to yield, the cost of the person, device security and product.
The reaction of ring manganese is the second step reaction during MMT, CMT produce, and generally in reactor, under air-tight state, carries out chemical reaction.But, in the time adding material to carry out chemical reaction in reactor, must open the drop out line valve of reactor or open the charge door (normally hand hole, manhole etc.) of reactor, to keep the outer atmospheric pressure of still internal pressure and still to equate, inevitably want in this case ingress of air, so should manage air drive out of or do not allow air enter in still in order to realize anhydrous and oxygen-free operating condition in still.In conventional method, no matter be reactor is replaced repeatedly or reactor is vacuumized and uses nitrogen replacement again with nitrogen, or to methods such as the steam on reactor heating eliminating still wall, there is very large defect in these ways.Be mainly because reactor turnover material cause still internal pressure slightly change, even because cold and hot mixing of materials causes still temperature fluctuation, still internal gas pressure also can produce slight variation owing to expanding with heat and contract with cold, like this in still internal pressure during lower than ambient pressure, still outer air will (as the blow-down pipe of reactor) " suck-back " enter in still along the position communicating with air, thereby need to increase displacement number of times, the consumption of nitrogen is larger, and energy consumption is also high.In actual production, operating personnel, often to " suck-back " air in still and ignorant, cause and react unsuccessfully, affect commercial plant normally to move, and have caused huge economic loss.
Summary of the invention
The present invention will overcome the deficiencies in the prior art exactly, and a kind of industrial anhydrous and oxygen-free technology is provided, and solves " suck-back " problem, to meet the anhydrous and oxygen-free environmental demand in the chemical process such as MMT, CMT; This technology can make reactor with trying one's best few inert gas, and completes turnover material under its protection, reduces the risk that reaction is failed.
Principle of the present invention is in Chemical Manufacture, while needing the reactor charging of anhydrous and oxygen-free operation, makes in reactor under the protection in inert gas all the time, and makes to remain in still slight positive pressure state; Specifically realize by following steps:
(1), pressure-fired single breathing valve is installed on the vent line of reactor, and maintain before charging and be slight positive pressure state in reactor by being filled with inert gas; Described pressure-fired is the malleation that gauge pressure is not more than 400Kpa;
(2), in reactor, be filled with micrometeor inert gas by small-range flowmeter, then open charge door and feed intake, remain in still and have inert gas to flow out outside still; The flow-control of described inert gas is at 20 ~ 200 liters/min.Specifically, exactly by installing and can measure the small-range flowmeter system assembly of micrometeor, control inert gas flow, recommend adoption spinner flowmeter with control method manually or automatically on gas inlet wire; In the time of material feeding (particularly to reactor reinforcing body material time), first open again charge door to passing into inert gas in still, ensure that by flowmeter control air inflow the lasting micrometeor of inert gas enters, close charge door until complete charging.
Above-mentioned inert gas refers to chemical property torpescence, comparatively stable gas, as: helium, nitrogen, argon gas etc.In cost consideration, industrial conventionally using nitrogen as inert gas, require nitrogen gas purity more high better, be preferably purity and be not less than 99.999% high-purity nitrogen.
Above-mentioned pressure-fired refers to that gauge pressure is that 0 ~ 400Kpa(is not containing 0), being particularly suitable for pressure is 0.001 ~ 10KPa.
Breather valve is in general sense a kind of safety means, Main Function is to prevent the interior superpressure of container (great majority for storage tank) and prevent that container from being taken out flat, and pressure-fired single breathing valve in the present invention refers to that a kind of gas unidirectional circulation valve (can buy in accessory shop and obtain, or can be tailor-made to valve plant on request), by this valve installation on the vent line of reactor, make gas can only by reactor to outer circulation, and can not ecto-entad circulation.And this valve outwards opening pressure of circulation can artificially be set, and is generally set as pressure-fired, as 100KPa, 20KPa, 5 KPa etc.When still internal pressure is during lower than this pressure-fired, pressure-fired single breathing valve will be closed, and cut off gas communication.
Below above-mentioned anhydrous and oxygen-free method of operating is applied in the ring manganese reaction production technology of methyl cyclopentadienyl manganese, the operating procedure of ring manganese reaction is as follows:
(a) after encircling manganese in reactor and having reacted, in still, be filled with certain inert gas, be elevated to after 0.2～0.3MPa until still internal pressure, open still outlet valve, reactant liquor is discharged to reactor by discharging pipeline, until reactor is emptying and pressure drop to pressure-fired, then close outlet valve and keep reactor pressure-fired, prepare to enter next ring manganese reaction cycle;
(b), by being filled with micrometeor inert gas in small-range flowmeter and inert gas tube alignment still, and then open charge door, in still, add solid material anhydrous Manganese chloride; Then close charge door, and close inert gas pipeline simultaneously;
(c), open blow-down pipe with and on pressure-fired single breathing valve, open again the related valve on liquid material feeding line, the reaction solution of last process ring sodium reaction is pressed in reactor with inert gas, in the time that still internal pressure is down to pressure-fired, closes blow-down pipe and pressure-fired single breathing valve; Then open stirring system, make the interior mixing of materials of still even; Reactor is warming up to 130～160 DEG C, reacts 1 ~ 3 hour;
(d), repeating step (a), thereby complete a secondary ring manganese reaction time.
The opening pressure of the single breathing valve of pressure-fired described in such scheme 8 is preferably 20Kpa; The flow of small-range spinner flowmeter control micrometeor nitrogen is preferably 70 liters/min.
The present invention has the following advantages compared with conventional anhydrous and oxygen-free technology:
(1) method that the present invention vacuumizes filling with inert gas displacement with respect to needs again has simple to operate, only need to be filled with step of inert gas, and can prevent that the part that likely communicates with air because of reactor from leaking suck air because poorly sealed generation appears in valve, flange gasket fault, and do not need the equipment investments such as vavuum pump less yet;
(2) the present invention adds pressure-fired single breathing valve can ensure pressure-fired in still, and the situation such as maloperation that prevents personnel causes oxygen diffusion to enter in still while causing still internal and external pressure balance; And temperature in the kettle changes and the situation of the suck-back air that causes;
(3) the present invention's method that tradition is repeatedly replaced with inert gas relatively, passes into inert gas with small-range flowmeter control micrometeor while only needing charging, can reduce the number of operations of inert gas replacement reactor and reduce inert gas consumption.
(4) because this programme has been separated soon " suck-back " problem well, greatly improved and be reacted into power (rate of good) and product yield, obtained good economic benefit.
Brief description of the drawings
Accompanying drawing is structure and the pipeline connection diagram of ring manganese reactor;
In figure: 1, discharging pipeline, 2, heating jacket, 3, reactor, 4, solid material charge door, 5, liquid material feeding line, 6, small-range spinner flowmeter, 7, inert gas enters pipeline, 8, pressure-fired single breathing valve, 9, blow-down pipe, HOS, conduction oil confession, HOR, conduction oil return, FIQ, flow indication accumulation.
Detailed description of the invention
To produce the reaction (being called for short: the reaction of ring manganese) of methyl cyclopentadienyl manganese, as example, the present invention is further described below, but be not the restriction to range of application of the present invention.
Ring manganese reactive chemistry equation is:
2（C
6H
7）Na?+?MnCl
2?→(C
6H
7)
2Mn?+?2NaCl↓
That is: in ether solvent, 204 parts of methyl cyclopentadienyl sodium react with 126 parts of anhydrous Manganese chloride, generate 213 parts of methyl cyclopentadienyl manganese and 117 parts of sodium chloride.The quantity of ether solvent equals to encircle amount of solvents in sodium reaction.
Embodiment 1
A ring manganese reaction production technology for methyl cyclopentadienyl manganese, its processing step is as follows:
(a) after encircling manganese in reactor 3 and having reacted, in still, be filled with certain high pure nitrogen, be elevated to after 0.2～0.3MPa until still internal pressure, open still outlet valve, reactant liquor is discharged to reactor 3 by discharging pipeline 1, until reactor is emptying and pressure drop to pressure-fired, then close outlet valve and keep reactor pressure-fired and nitrogen atmosphere, prepare to enter next ring manganese reaction cycle;
(b), in still, be filled with micrometeor high pure nitrogen by small-range flowmeter 6 and inert gas inleting pipe line 7, small-range spinner flowmeter 6 is controlled micrometeor high pure nitrogen flow at 70 liters/min, to maintain atmosphere of inert gases; And then open solid material charge door 4, in still, add solid material anhydrous Manganese chloride (the present embodiment addition is 390kg); Then close solid material charge door, and close inert gas inleting pipe line 7 simultaneously;
(c), open blow-down pipe 9 with and on pressure-fired single breathing valve 8, and to regulate the opening pressure of pressure-fired single breathing valve 8 be that 0.02MPa(is 20KPa); Open again the related valve on liquid material feeding line 5, with high pure nitrogen, by the reaction solution of last process ring sodium reaction, (this reactant liquor mainly comprises methyl cyclopentadienyl sodium and ether solvent, the quantity of reactant liquor is determined according to the stoichiometric coefficient of each material in chemical equation, those skilled in the art just can be determined by calculating) be pressed in reactor 3, in the time that still internal pressure is down to pressure-fired, close blow-down pipe 9 and pressure-fired single breathing valve 8; Then open stirring system, make the interior mixing of materials of still even; By heating jacket 2, reactor is warming up to 130～160 DEG C, reacts 1 ~ 3 hour;
(d), repeating step (a), thereby complete a secondary ring manganese reaction time.
Embodiment 2
A ring manganese reaction production technology for methyl cyclopentadienyl manganese, keeps, on basis that embodiment 1 other steps and technological parameter are constant, only changing inert gas into helium by high pure nitrogen.
Example 3-10
A kind of ring manganese reaction production technology of methyl cyclopentadienyl manganese, on embodiment 1 basis, keep other steps and technological parameter constant, difference is only that pressure-fired single breathing valve 8 adopts different opening pressure (being the different scope of pressure-fired control) and small-range spinner flowmeter 6 to adopt different micrometeors, and concrete condition is in table 1.
Reference examples 1
A kind of ring manganese reaction production technology (technique before improving) of methyl cyclopentadienyl manganese, its processing step is as follows:
As shown in drawings, remove small-range spinner flowmeter 6 and pressure-fired single breathing valve 8 and relevant valve in figure, and replace the part of removing with pipeline, just form the process flow diagram of this reference examples.
(a) after encircling manganese in reactor 3 and having reacted, in still, be filled with certain high pure nitrogen, be elevated to after 0.2～0.3MPa until still internal pressure, open still outlet valve, reactant liquor is discharged to reactor 3 by discharging pipeline 1, until reactor is emptying and pressure drop to normal pressure (referring to atmospheric pressure balance outside still internal pressure and still), then quick closedown outlet valve, prepares to enter next ring manganese reaction cycle;
(b), open solid material charge door 4, in still, add solid material anhydrous Manganese chloride (this reference examples addition is 390kg); Then close solid material charge door, leave standstill 30 minutes;
(c) nitrogen replacement: be filled with high pure nitrogen by inert gas inleting pipe line 7 in still, be elevated to after 0.2～0.3MPa until still internal pressure, close air inlet and open blow-down pipe 9, nitrogen in still is emitted, until still internal pressure drops to normal pressure, close drop out line, thereby complete nitrogen replacement process one time; So altogether to carry out 3 to 5 conversions;
(d), open blow-down pipe 9, open again the related valve on liquid material feeding line 5, with high pure nitrogen, by the reaction solution of last process ring sodium reaction, (this reactant liquor mainly comprises methyl cyclopentadienyl sodium and ether solvent, the quantity of reactant liquor is determined according to the stoichiometric coefficient of each material in chemical equation, and those skilled in the art can pass through calculative determination.) be pressed in reactor 3; Then open stirring system, make the interior mixing of materials of still even; By heating jacket 2, reactor is warming up to 130～160 DEG C, reacts 1 ~ 3 hour;
(e), repeating step (a), thereby complete a secondary ring manganese reaction time.
Below the ring manganese reaction implementation result that adopts anaerobic waterless operation of the present invention is analyzed: methyl cyclopentyl-dialkyl-tricarbon manganium (MMT) needs three-step reaction in producing, and encircles sodium reaction, the reaction of ring manganese and carbonylation; Wherein encircling manganese reaction is second step reaction wherein, because the reaction effect of this step of independent measurement is very difficult, therefore the present invention is to embody by the total yield of products after overall three-step reaction and reaction rate of good by implementation result, also just say, by keeping reactions steps and the technological parameter of the reaction of first step ring sodium and the 3rd carbonylation constant, only change the part process of second step ring manganese reaction, finally determine the reaction effect of second step ring manganese reaction by the technical indicator of final products.
Respectively the technique of the reaction of ring sodium and carbonylation is briefly described below, detailed technical process is prior art, exceeds and repeats at this.
1, the reaction of ring sodium is as follows:
2C
6H
8?+?2Na?→2（C
6H
7）Na?+2?H
2↑
That is: taking ether solvent as medium, methyl cyclopentadiene reacts with sodium metal, produces methyl cyclopentadienyl sodium and hydrogen.Describe by stoichiometric coefficient: 160 parts of methyl cyclopentadiene+46 part sodium metals carry out chemical reaction, generate 204 parts of methyl cyclopentadienyl sodium and 4 parts of hydrogen.
2, carbonylation is as follows:
(C
6H
7)
2Mn?+?3CO?→(C
6H
7)Mn(CO)
3?+?C
6H
7·
That is: taking ether solvent as medium, 213 parts of methyl cyclopentadienyl manganese+84 part carbon monoxide carry out chemical reaction, generate 218 parts of methyl cyclopentadiene three carbon back manganese and 79 methyl cyclopentadiene free radicals.Wherein methyl cyclopentadiene free radical will be polymerized to high polymer.
More than the ether solvent in reaction time adds in the reaction of ring sodium, quantity is methyl cyclopentadiene 5 to 7 times, and do not need to add again solvent when the reaction of ring manganese, carbonylation.
Below in conjunction with the ring manganese reaction of embodiment 1-10 and the above-mentioned reaction of ring sodium, carbonylation, by the contrast of total yield of products after three-step reaction and reaction rate of good and reference examples 1, embody implementation result of the present invention (encircling the reaction effect of manganese reaction); Wherein overall yield of reaction refers to that actual product output accounts for the percentage of complete reaction theoretical yield, and methyl cyclopentyl-dialkyl-tricarbon manganium is with respect to the yield of manganese chloride; Reaction rate of good refer to after overall three-step reaction, product in carbonylation liquid (MMT) concentration is greater than 15%(mass ratio) reaction batch account for the percentage of total batch.
Through calculating, the total recovery of reference examples 1 is 70%, and reaction rate of good is 90%; And the total recovery of embodiment 1 has improved 2%, reaction rate of good has improved 5%; The total recovery of embodiment 2 has improved 3%, and reaction rate of good has improved 7%; The concrete condition of embodiment 3-10 is in table 1; Comprehensive more known embodiment 2 is best embodiment.
The control parameter of table one, embodiment 3-10 and technology index data table
By the contrast of above embodiment and technical indicator, the present invention can realization response still in best anhydrous and oxygen-free environment, increase substantially the reaction rate of good of ring manganese reaction and the total recovery of product; And those skilled in the art are to be understood that, above embodiment is only several exemplary embodiments of the present invention, in the situation that not exceeding or do not depart from protection domain of the present invention, technical solutions and their implementation methods of the present invention have multiple modification, improvement or equivalent variations, and these all should fall within the scope of protection of the present invention; And above embodiment is only the application of this anhydrous and oxygen-free method of operating in the reaction of ring manganese, but the application of the method is not limited to this field, after the suitable adjustment of making according to actual conditions through those skilled in the art, this method can be applied in other Chemical Manufacture that need anhydrous and oxygen-free environment too, and obtains the good reaction effect of precognition.
Claims (5)
1. a method that realizes anhydrous and oxygen-free operation, is characterized in that, comprises the following steps:
(1), pressure-fired single breathing valve is installed on the vent line of reactor, and maintain before charging and be slight positive pressure state in reactor by being filled with inert gas; Described pressure-fired is the malleation that gauge pressure is not more than 400Kpa;
(2), in reactor, be filled with micrometeor inert gas by small-range flowmeter, then open charge door and feed intake, remain in still and have inert gas to flow out outside still; The flow-control of described inert gas is at 20 ~ 200 liters/min.
2. the method that realizes anhydrous and oxygen-free operation according to claim 1, is characterized in that, described pressure-fired is gauge pressure 0.001 ~ 10KPa.
3. the method that realizes anhydrous and oxygen-free operation according to claim 1, is characterized in that, described inert gas is that purity is not less than 99.999% high pure nitrogen.
4. application rights requires a ring manganese reaction production technology for the methyl cyclopentadienyl manganese of the arbitrary described anhydrous and oxygen-free method of operating of 1-3, it is characterized in that, the operating procedure of ring manganese reaction is as follows:
(a) after encircling manganese in reactor and having reacted, in still, be filled with certain inert gas, be elevated to after 0.2～0.3MPa until still internal pressure, open still outlet valve, reactant liquor is discharged to reactor by discharging pipeline, until reactor is emptying and pressure drop to pressure-fired, then close outlet valve and keep reactor pressure-fired, prepare to enter next ring manganese reaction cycle;
(b), by being filled with micrometeor inert gas in small-range flowmeter and inert gas tube alignment still, and then open charge door, in still, add solid material anhydrous Manganese chloride; Then close charge door, and close inert gas pipeline simultaneously;
(c), open blow-down pipe with and on pressure-fired single breathing valve, open again the related valve on liquid material feeding line, the reaction solution of last process ring sodium reaction is pressed in reactor with inert gas, in the time that still internal pressure is down to pressure-fired, closes blow-down pipe and pressure-fired single breathing valve; Then open stirring system, make the interior mixing of materials of still even; Reactor is warming up to 130～160 DEG C, reacts 1 ~ 3 hour;
(d), repeating step (a), thereby complete a secondary ring manganese reaction time.
5. the ring manganese of methyl cyclopentadienyl manganese according to claim 4 reaction production technology, is characterized in that, the opening pressure of described pressure-fired single breathing valve 8 is 20Kpa; The flow of described small-range spinner flowmeter control micrometeor nitrogen is 70 liters/min.
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| CN109806830A (en) * | 2019-03-14 | 2019-05-28 | 郑州轻工业学院 | A kind of anhydrous and oxygen-free reaction unit and its application |
| CN110180470A (en) * | 2019-04-29 | 2019-08-30 | 中国科学院山西煤炭化学研究所 | A kind of continuous paste state bed reactor of autoclave and its application method |
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| CN110180470A (en) * | 2019-04-29 | 2019-08-30 | 中国科学院山西煤炭化学研究所 | A kind of continuous paste state bed reactor of autoclave and its application method |
| CN110180470B (en) * | 2019-04-29 | 2024-01-26 | 中国科学院山西煤炭化学研究所 | Kettle type continuous slurry bed reactor and use method thereof |
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