CN1298695C - Gas phase chlorination method and device for preparing chloro-formic acid-1-chloro-formic ester - Google Patents
Gas phase chlorination method and device for preparing chloro-formic acid-1-chloro-formic ester Download PDFInfo
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- CN1298695C CN1298695C CNB200410015971XA CN200410015971A CN1298695C CN 1298695 C CN1298695 C CN 1298695C CN B200410015971X A CNB200410015971X A CN B200410015971XA CN 200410015971 A CN200410015971 A CN 200410015971A CN 1298695 C CN1298695 C CN 1298695C
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Abstract
The present invention relates to a method for preparing chlorocarbonic acid-1-chloromethyl ester through gas phase chlorination reaction. The method comprises: methyl chloroformate is used as raw materials to carry out gas phase chlorination reaction with chlorine gas in the mixed gas of chlorine gas and inert gas by heating under visual light, wherein the molar ratio of methyl chloroformate to chlorine gas is 1:0.1 to 1.5. The present invention also relates to a device for preparing chlorocarbonic acid-1-chloromethyl ester through gas phase chlorination reaction. The method of the present invention has the advantages of convenient and feasible operation, simple and convenient device, low cost and high yield, and therefore, the present invention is convenient to industrialization production.
Description
Technical field
The present invention relates to a kind of method and apparatus for preparing chloroformic acid-1-chloromethyl ester that reacts through gas phase chlorination.
Background technology
At Olofson, R.A. and Martz have disclosed among the DE.3241568 of J.T (1983) with formaldehyde photoreactive gas (COCl
2) react the method for preparing chloroformic acid chloro methyl esters, use PhCH
2Bu
3NCl is during as catalyzer, and yield is 42%; With [(Bu
2N)
2CCl]
+Cl
-During as catalyzer, yield can bring up to 91.5%, but used phosgene is quite dangerous, is unsuitable for suitability for industrialized production, and the catalyst system therefor costliness, also is not suitable for industrialization.
At Sekine, disclosed among people's such as Yasuo the JP08040986 (1996) and used ClCO
2Me and SO
2Cl
2Reaction prepares ClCOCH
2The method of Cl, but product does not separate.
In people's such as Moqyorodi Ferenc DE.3826584 (1989), disclosed employing ClCOCH
3And Cl
2Prepare ClCOCH by the chlorination of liquid phase light
2The method of Cl, wherein use up is visible light, by the Cl in the control feeding reaction solution
2Amount, control transforms.When transformation efficiency is 40%, ClCOOCH
2The Cl selectivity can reach 99.7%, yield 98%; When transformation efficiency is 88%, ClCOOCH
2Cl content is 70.5%, and yield is 61.9%, dichloro-by-products content 29.6%, yield 26%; When transformation efficiency is 96%, ClCO
2CH
2Cl content 63.8%, yield 61.2%, dichloro by-products content are 33.9%, yield 32.5%, three chloro by-products content 2.4%, yield 23%.The liquid phase chlorination reaction improves ClCO by the control transformation efficiency
2CH
2The content of Cl, it is lower to be easy to generate production efficiency, and the yield of primary first-order equation is less than 40%, and the recycling of raw material needs more equipment.
Therefore, need a kind of like this method for preparing chloroformic acid-1-chloromethyl ester, it can make product one chloro methyl esters separate with chlorine, avoids the carrying out of many chlorinations, and reaction efficiency is improved.
Summary of the invention
The method and apparatus that the purpose of this invention is to provide a kind of simple and easy to do, easy industrialization, cost is lower and by product is less, transformation efficiency is higher preparation chloroformic acid-1-chloro ester.
At the problem that exists in the prior art, the invention provides the method for a kind of gas phase chlorination prepared in reaction chloroformic acid-1-chloromethyl ester, it is included under the visible light, under heating, be that chlorine in the mixed gas of raw material and chlorine and rare gas element carries out gas phase chlorination reaction, wherein methyl-chloroformate with the methyl-chloroformate: the mol ratio of chlorine is 1: 0.1-1.5, and Heating temperature is 60-130 ℃, the temperature of gas phase chlorination reaction is 60-105 ℃, and the reaction times is 1-24 hour.In the mixed gas of described chlorine and rare gas element, the content of rare gas element accounts for the 0-90 mole % of mixed gas total amount, and described rare gas element is one or more gases that are selected from nitrogen, helium and the argon gas.
The present invention also provides a kind of device that is used for gas phase chlorination prepared in reaction chloroformic acid-1-chloromethyl ester, it comprises reactor 1, wrap in reactor heater block 2 on every side and the Gas-phase reactor 3 that is inserted on the reactor, wherein said Gas-phase reactor comprises gas phase chlorination conversion zone 5 and the reflux condensation mode section 6 on the gas phase chlorination conversion zone.Between described reactor and described Gas-phase reactor, also has packing section 4.In the gas phase chlorination conversion zone of described reactor and described Gas-phase reactor, also insert thermometer T1 and the T2 that is used to measure liquidus temperature and gas phase temperature.Device of the present invention can comprise 1-5 Gas-phase reactor.And described Gas-phase reactor is made with glass, silica glass, pottery or enamel.
Description of drawings
Fig. 1 is the used device of method of implementing gas phase chlorination prepared in reaction chloroformic acid of the present invention-1-chloromethyl ester.
Embodiment
Particularly, the invention provides the method for a kind of gas phase chlorination prepared in reaction chloroformic acid-1-chloromethyl ester, it is at visible light, under the illumination as daylight or fluorescent lamp, under heating, be that chlorine in the mixed gas of raw material and chlorine and rare gas element carries out the gas phase chlorination reaction with the methyl-chloroformate, concrete reaction formula is as follows:
In above-mentioned reaction, elder generation's heating raw liquid chlorine methyl-formiate, make its gasification, used Heating temperature is 60-130 ℃, is preferably 70-100 ℃, methyl-chloroformate after the gasification and chlorine carry out the gas phase chlorination reaction, used gas phase chlorination temperature of reaction is 60-105 ℃, is preferably 70-80 ℃, and the boiling point of the product chloroformic acid-1-chloromethyl ester of generation is 103 ℃, this product becomes liquid under reaction conditions of the present invention, away from chlorination reaction region.
React used another kind of raw material in the present invention, be in the mixed gas of chlorine and rare gas element, the content of described rare gas element accounts for the 0-90 mole % of mixed gas total amount, be preferably 20-50 mole %, that is to say, this kind raw material can be pure chlorine, also can be the mixed gas of chlorine and rare gas element, and rare gas element does not participate in reaction.Rare gas element can be one or more the mixing in the gases such as nitrogen, helium, argon gas.
To react after the above-mentioned two kinds of raw materials mixing of the present invention, wherein methyl-chloroformate: the mol ratio of chlorine is 1: 0.1-1.5 is preferably 1: 0.15-0.43.
Usually, the flow of input unstripped gas can be controlled by the rate of heating of raw material or the input of raw material, and in general, the volumetric flow rate of mixed raw material gas is 0.1-1L/min.In the present invention, to reaction pressure and without particular limitation, be generally normal pressure.Reaction times is then relevant with the size and the raw material in the reactor of reactor, is generally 1-24 hour, but with 3-10 hour for well.
The used gas phase chlorination reaction unit of the present invention is a kind of special device, as shown in Figure 1, it by raw material still or reactor 1, wrap in the heater block 2 around the reactor 1 and the Gas-phase reactor 3 that is inserted on the reactor is formed.In described reactor 1, add raw material, i.e. liquid chlorine methyl-formiate, this raw material gasifies by heater block 2 heating that wrap in around the reactor 1, and amount of vaporization can be controlled by Heating temperature.Described heater block 2 can be a kind of heating jacket, and at the hot steam of end feeding of chuck, the steam that the other end output is cold so circulates, and reaches the purpose of heating.Also can be equipped with packing section 4 between described reactor 1 and described Gas-phase reactor 3, this filler can be made of the porcelain ring, to guarantee fully separating of raw material and product.As shown in Figure 1, described Gas-phase reactor 3 comprises gas phase chlorination conversion zone 5 and reflux condensation mode section 6 thereon, another kind of raw material of the present invention, be of the bottom feeding of the mixed gas of chlorine and rare gas element from gas phase chlorination conversion zone 5, and in this section, carrying out the gas phase chlorination reaction, the prolong postcooling that reacted product gas rising runs in the reflux condensation mode section 6 becomes liquid, in reflux condensation mode section 6, water coolant is fed by the bottom of reflux condensing tube, to reach cooling purpose.In device of the present invention, in the gas phase chlorination conversion zone 5 of described reactor 1 and described Gas-phase reactor 3, also insert thermometer T1 and the T2 that is used to measure liquidus temperature and gas phase temperature, with the Heating temperature of control reactor and the temperature of gas phase chlorination reaction.The material of Gas-phase reactor 3 can be general glass, also can be silica glass, pottery or enamel.For different raw materials, Gas-phase reactor need be furnished with different heat-eliminating mediums, and heat-eliminating medium can be a water-cooled, also fan can be installed around reactor.Gas-phase reactor does not need to be equipped with special ultraviolet source, and usually indoor visible light or fluorescent lamp can guarantee that chlorination carries out.In addition, can also be equipped with 1-5 Gas-phase reactor,, raise the efficiency to increase speed of response according to the reactor size.
Compared with the prior art, effect of the present invention is significant beyond doubt.At first, the present invention carries out gas phase illumination chlorination reaction by methyl-chloroformate steam and chlorine, utilize the boiling point of raw material and product different, a chloro-product is separated with chlorine, avoid the carrying out of many chlorinations, thereby highly selective generates product chloroformic acid-1-chloromethyl ester, in general, utilize method and apparatus of the present invention, the above methyl-chloroformate of 85-95% is chlorinated fully is chloroformic acid-1-chloromethyl ester, and have only few many chloros by product to produce, so reaction efficiency is high.Secondly, the present invention adopts the gas phase chlorination method, do not need special ultraviolet source, just can carry out chlorination reaction under indoor general visible light, the product chloroformic acid-1-chloromethyl ester of formation passes back into raw material still or reactor immediately, so circulation, required is easy to operation, used equipment is simple and convenient, and cost is lower, so be convenient to suitability for industrialized production.
Embodiment
Below, the present invention is further detailed explanation in conjunction with the embodiments, but what should understand is that the present invention is not limited to these specific embodiments.
In the following embodiments, used raw material all can be buied on market.Used gas chromatograph is: GC-14B (model).
Embodiment 1
With 300kg methyl-chloroformate (3.2 * 10
3Mol) inject 500 liters of reactors, feed high-purity N
2Oxygen in the replacement(metathesis)reaction system, open then and stir, heating, the system for the treatment of refluxes when stablizing, and this moment, reactor liquidus temperature T1 was 68 ℃, and reactor gas phase temperature T2 is 68 ℃, slowly open the chlorine valve and feed chlorine, this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas was acid.The control rate of heating makes backflow moderate, controls chlorine flowrate simultaneously, makes speed of response too inviolent, and control gas-phase reaction temperature T 2 is 105 ℃.Along with the carrying out of chlorination reaction, reactor temperature T1 can constantly raise, and stopped reaction when treating that still internal heating temperature rises to 102 ℃ feeds 104.5 liters of chlorine (about 4.8 * 10 altogether in whole process
3Mol), the totally 1 hour reaction times.Sampling send GC to analyze each component content (weight %) in the reaction solution: unreacted raw material methyl-chloroformate 5.8%, and product chloroformic acid-1-chloromethyl ester 85.7%, by product dichloride 1.6%, other is 6.9% years old.Atmospheric distillation is used less than 103 ℃ of fraction recovery sets; Collecting 103-105 ℃ of fraction is product chloroformic acid-1-chloromethyl ester, and the GC purity assay is 97%; Greater than 105 ℃ of fractions is the dichloro-by product.
Embodiment 2
With 300kg methyl-chloroformate (3.2 * 10
3Mol) inject 500 liters of reactors, feed high-purity N
2Oxygen in the replacement(metathesis)reaction system, open then and stir, heating, the system for the treatment of refluxes when stablizing, and this moment, reactor liquidus temperature T1 was 60 ℃, reactor gas phase temperature T2 is 60 ℃, slowly open the mixed gas that the chlorine valve feeds chlorine and nitrogen, wherein nitrogen accounts for the 90mol% of mixed gas total amount, and this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas is acid.The control rate of heating makes backflow moderate, controls chlorine flowrate simultaneously, makes speed of response too inviolent, and control gas-phase reaction temperature T 2 is 100 ℃.Along with the carrying out of chlorination reaction, reactor temperature T1 can constantly raise, and stopped reaction when treating that still internal heating temperature rises to 130 ℃ feeds 6.97 liters of chlorine (about 0.32 * 10 altogether in whole process
3Mol), the totally 24 hours reaction times.Sampling send GC to analyze each component content (weight %) in the reaction solution: unreacted raw material methyl-chloroformate 3.5%, and product chloroformic acid-1-chloromethyl ester 91.3%, by product dichloride 2.6%, other is 2.6% years old.Atmospheric distillation is used less than 103 ℃ of fraction recovery sets; Collecting 103-105 ℃ of fraction is product chloroformic acid-1-chloromethyl ester, and the GC purity assay is 96%; Greater than 105 ℃ of fractions is the dichloro-by product.
Embodiment 3
With 300kg methyl-chloroformate (3.2 * 10
3Mol) inject 500 liters of reactors, feed high-purity N
2Oxygen in the replacement(metathesis)reaction system, open then and stir, heating, the system for the treatment of refluxes when stablizing, and this moment, reactor liquidus temperature T1 was 68 ℃, and reactor gas phase temperature T2 is 68 ℃, slowly open the chlorine valve and feed chlorine, this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas was acid.The control rate of heating makes backflow moderate, controls chlorine flowrate simultaneously, makes speed of response too inviolent, and control gas-phase reaction temperature T 2 is 95 ℃.Along with the carrying out of chlorination reaction, reactor temperature T1 can constantly raise, and stopped reaction when treating that still internal heating temperature rises to 102 ℃ feeds 20.9 liters of chlorine (about 0.96 * 10 altogether in whole process
3Mol), the totally 10 hours reaction times.Sampling send GC to analyze each component content (weight %) in the reaction solution: unreacted raw material methyl-chloroformate 3.3%, and product chloroformic acid-1-chloromethyl ester 90.8%, by product dichloride 2.9%, other is 3% years old.Atmospheric distillation is used less than 103 ℃ of fraction recovery sets; Collecting 103-105 ℃ of fraction is product chloroformic acid-1-chloromethyl ester, and the GC purity assay is 98%; Greater than 105 ℃ of fractions is the dichloro-by product.
Embodiment 4
With 300kg methyl-chloroformate (3.2 * 10
3Mol) inject 500 liters of reactors, feed high-purity N
2Oxygen in the replacement(metathesis)reaction system, open then and stir, heating, the system for the treatment of refluxes when stablizing, and this moment, reactor liquidus temperature T1 was 68 ℃, reactor gas phase temperature T2 is 68 ℃, slowly open the mixed gas that the chlorine valve feeds chlorine and helium, wherein helium accounts for the 50mol% of mixed gas total amount, and this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas is acid.The control rate of heating makes backflow moderate, controls chlorine flowrate simultaneously, makes speed of response too inviolent, and control gas-phase reaction temperature T 2 is 100 ℃.Along with the carrying out of chlorination reaction, reactor temperature T1 can constantly raise, and stopped reaction when treating that still internal heating temperature rises to 102 ℃ feeds 34.8 liters of chlorine (about 1.6 * 10 altogether in whole process
3Mol), the totally 18 hours reaction times.Sampling send GC to analyze each component content (weight %) in the reaction solution: unreacted raw material methyl-chloroformate 3.2%, and product chloroformic acid-1-chloromethyl ester 90.3%, by product dichloride 3.1%, other is 3.4% years old.Atmospheric distillation is used less than 103 ℃ of fraction recovery sets; Collecting 103-105 ℃ of fraction is product chloroformic acid-1-chloromethyl ester, and the GC purity assay is 95%; Greater than 105 ℃ of fractions is the dichloro-by product.
Embodiment 5
With 300kg methyl-chloroformate (3.2 * 10
3Mol) inject 500 liters of reactors, feed high-purity N
2Oxygen in the replacement(metathesis)reaction system, open then and stir, heating, the system for the treatment of refluxes when stablizing, and this moment, reactor liquidus temperature T1 was 68 ℃, reactor gas phase temperature T2 is 68 ℃, slowly open the mixed gas that the chlorine valve feeds chlorine and argon gas, wherein argon gas accounts for the 40mol% of mixed gas total amount, and this moment, chlorination reaction was promptly carried out rapidly, have oily matter to occur simultaneously on the wall of Gas-phase reactor, and tail gas is acid.The control rate of heating makes backflow moderate, controls chlorine flowrate simultaneously, makes speed of response too inviolent, and control gas-phase reaction temperature T 2 is 95 ℃.Along with the carrying out of chlorination reaction, reactor temperature T1 can constantly raise, and stopped reaction when treating that still internal heating temperature rises to 102 ℃ feeds 48.8 liters of chlorine (about 2.24 * 10 altogether in whole process
3Mol), the totally 20 hours reaction times.Sampling send GC to analyze each component content (weight %) in the reaction solution: unreacted raw material methyl-chloroformate 2.4%, and product chloroformic acid-1-chloromethyl ester 87.6%, by product dichloride 7.6%, other is 2.4% years old.Atmospheric distillation is used less than 103 ℃ of fraction recovery sets; Collecting 103-105 ℃ of fraction is product chloroformic acid-1-chloromethyl ester, and the GC purity assay is 99%; Greater than 105 ℃ of fractions is the dichloro-by product.
Although the specific embodiment of the present invention has been done detailed explanation and description, but what should understand is, under the situation that does not depart from claim scope of the present invention, can be in form and in fact the present invention is made improvements and change, but they are all within the scope of the invention.
Claims (8)
1. the method for gas phase chlorination prepared in reaction chloroformic acid-1-chloromethyl ester, it is included under the visible light, under heating, be that chlorine in the mixed gas of raw material and chlorine and rare gas element carries out the gas phase chlorination reaction with the methyl-chloroformate, in described reaction, methyl-chloroformate is heated to gasification, gas methyl-chloroformate after the gasification enters into reaction zone and chlorine reaction, product chloroformic acid-1-the chloromethyl ester that generates becomes liquid, away from reaction zone, methyl-chloroformate wherein: the mol ratio of chlorine is 1: 0.1-1.5.
2. the method for claim 1, wherein Heating temperature is 60-130 ℃, and the temperature of gas phase chlorination reaction is 60-105 ℃, and the reaction times is 1-24 hour.
3. method as claimed in claim 1 or 2, wherein the molar content of rare gas element accounts for the 0-90% of mixed gas total amount in the mixed gas of described chlorine and rare gas element.
4. method as claimed in claim 1 or 2, wherein said rare gas element are one or more gases that are selected from nitrogen, helium and the argon gas.
5. device that is used for gas phase chlorination prepared in reaction chloroformic acid-1-chloromethyl ester, it comprises reactor (1), wrap in the heater block (2) around the reactor and be inserted in Gas-phase reactor (3) on the reactor, wherein said Gas-phase reactor comprises gas phase chlorination conversion zone (5) and the reflux condensation mode section (6) on this gas phase chlorination conversion zone, in described gas phase chlorination conversion zone, insert the thermometer T2 that is used to measure the gas-phase reaction temperature, between described reactor and described Gas-phase reactor, also have the packing section (4) that constitutes by the porcelain ring.
6. device as claimed in claim 5 wherein also inserts the thermometer T1 that is used to measure liquidus temperature in described reactor.
7. device as claimed in claim 5, it comprises 1-5 Gas-phase reactor.
8. device as claimed in claim 5, wherein said Gas-phase reactor is made with glass, silica glass, pottery or enamel.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410015971XA CN1298695C (en) | 2004-01-19 | 2004-01-19 | Gas phase chlorination method and device for preparing chloro-formic acid-1-chloro-formic ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410015971XA CN1298695C (en) | 2004-01-19 | 2004-01-19 | Gas phase chlorination method and device for preparing chloro-formic acid-1-chloro-formic ester |
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| CN1298695C true CN1298695C (en) | 2007-02-07 |
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| CN109096111A (en) * | 2018-09-11 | 2018-12-28 | 安徽东至广信农化有限公司 | A kind of synthetic method of chloro-methyl-chloroformate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2108961A (en) * | 1981-11-10 | 1983-05-25 | Poudres & Explosifs Ste Nale | Preparation of chloromethyl chloroformate from formaldehyde and phosgene |
| DE3826584A1 (en) * | 1987-08-05 | 1989-02-16 | Eszakmagyar Vegyimuevek | Process and apparatus for the preparation of chlorinated chloroformates |
| CN1283625A (en) * | 2000-07-14 | 2001-02-14 | 中国科学院上海有机化学研究所 | Process and equipment for preparing chloromethyl trimethylsilane by gas-phase optical chlorinating reaction |
-
2004
- 2004-01-19 CN CNB200410015971XA patent/CN1298695C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2108961A (en) * | 1981-11-10 | 1983-05-25 | Poudres & Explosifs Ste Nale | Preparation of chloromethyl chloroformate from formaldehyde and phosgene |
| DE3826584A1 (en) * | 1987-08-05 | 1989-02-16 | Eszakmagyar Vegyimuevek | Process and apparatus for the preparation of chlorinated chloroformates |
| CN1283625A (en) * | 2000-07-14 | 2001-02-14 | 中国科学院上海有机化学研究所 | Process and equipment for preparing chloromethyl trimethylsilane by gas-phase optical chlorinating reaction |
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