CN1330615C - Process for production of hydrofluorocarbons, products thereof and use of the products - Google Patents
Process for production of hydrofluorocarbons, products thereof and use of the products Download PDFInfo
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- CN1330615C CN1330615C CNB2004800012200A CN200480001220A CN1330615C CN 1330615 C CN1330615 C CN 1330615C CN B2004800012200 A CNB2004800012200 A CN B2004800012200A CN 200480001220 A CN200480001220 A CN 200480001220A CN 1330615 C CN1330615 C CN 1330615C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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Abstract
A process which comprises reacting a halogenated methane mixture with hydrogen fluoride in a vapor phase in the presence of a fluorination catalyst in a single reaction zone, introducing the formed gas into a distilling column, and conducting the separation and purification of the gas therein to thereby obtain two or more hydrofluorocarbons. The process enables industrially advantageous production of hydrofluorocarbons useful as etching gas or cleaning gas in the production of semiconductor devices, particularly fluoromethane and difluoromethane, at high purity.
Description
Technical field
The present invention relates to the manufacture method of highly purified hydrogen fluorohydrocarbon, its goods and uses thereof.
Background technology
It is zero feature that hydrogen fluorohydrocarbon (following be called sometimes " HFC ") class has so-called ozone layer destroying coefficient, for example, 1,1,1,2-Tetrafluoroethane, pentafluoride ethane or methylene fluoride (following be called sometimes " HFC-32 ") are as the useful compound of refrigerant gas, and in addition, methyl fuoride (following be called sometimes " HFC-41 "), methylene fluoride and trifluoromethane (following be called sometimes " HFC-23 ") etc. are as the semi-conductor useful compound of etching gas.
Manufacture method as methylene fluoride, for example, known carrene (following be called sometimes " methylene dichloride ") or chlorofluoromethane (following be called sometimes " HCFC-31 ") and the hydrogen fluoride of making, in the presence of fluorination catalyst, the method of in gas phase, reacting (No. 2745886 specification sheets of United States Patent (USP), No. 3235612 specification sheets of United States Patent (USP)) etc., on the other hand, also knownly use antimony halides as the method (No. 2005711 specification sheets of United States Patent (USP)) of catalyzer etc., and any one all is the technical scheme that relates generally to catalyzer with liquid phase method.
Manufacture method as methyl fuoride, for example, known use chromium fluoride catalyzer makes methyl alcohol and hydrogen fluoride carry out fluoric method (spy opens flat 4-7330 communique) etc. in gas phase and make method (spy opens clear 60-13726 communique) that chloromethane and hydrogen fluoride reacts etc. in the presence of the chromium fluoride catalyzer in gas phase, but exists because of generating the corrosion that water caused or selecting the problem of rate variance etc.
In addition, as the manufacture method of the hydrogen fluorohydrocarbon more than 2 kinds or 2 kinds, for example, the known 2-chloro-1,1 that makes, 1-Halothane and hydrogen fluoride reaction, generate 1,1,1, the 2-Tetrafluoroethane, this 1,1,1, make the method (WO95/15937 communique) of methyl chloride and trieline and hydrogen fluoride reaction under the existence of 2-Tetrafluoroethane, make trieline and hydrogen fluoride reaction, generate 2-chloro-1,1, the 1-Halothane, make 2-chloro-1,1 then, 1-Halothane and hydrogen fluoride reaction generate 1,1,1, in the operation of 2-Tetrafluoroethane, for example by adding 2,2-two chloro-1,1,1-Halothane or 2-chloro-1,1,1, the 2-Tetrafluoroethane, make and generate 1,1,1, generate the method (the flat 7-507787 communique of special table) of pentafluoride ethane etc. in the time of the 2-Tetrafluoroethane, but above-mentioned any method all has two different reaction zones of reaction conditions (first reactor and second reactor), has the problem of uneconomical grade thus.
Summary of the invention
The present invention is the invention of finishing under such background, be can be industrial advantageously make highly purified hydrogen fluorohydrocarbon class, the particularly methyl fuoride that can be in the manufacturing engineering of semiconducter device uses as etching gas or purge gas, the method for methylene fluoride to provide, its goods and uses thereof are problem.
The present inventor, carried out deep research for solving above-mentioned problem, found that if adopt to contain uses methyl halide mixture and hydrogen fluoride as raw material, make them in gas phase, in the presence of fluorination catalyst, reaction in single reaction zone (reactor), after carrying out separation and purification in the gas importing distillation tower that generates, obtain the method for the operation of the hydrogen fluorohydrocarbon more than 2 kinds or 2 kinds, then can solve above-mentioned problem, and finish the present invention.
Therefore, the invention provides a kind of manufacture method of hydrogen fluorohydrocarbon, it is characterized in that, contain and make methyl halide mixture and hydrogen fluoride, in gas phase, in the presence of fluorination catalyst, in single reaction zone, react, after carrying out separation and purification in the gas importing distillation tower that generates, obtain the operation of the hydrogen fluorohydrocarbon more than 2 kinds or 2 kinds.
In addition, the invention provides a kind of methyl fuoride goods, it is characterized in that containing the purity of using above-mentioned manufacture method to obtain and be methyl fuoride more than or equal to 99.999% volume, or a kind of methylene fluoride goods are provided, it is characterized in that containing the purity of using above-mentioned manufacture method to obtain and be methylene fluoride more than or equal to 99.999% volume.
Further, the invention provides a kind of etching gas or purge gas, it is characterized in that containing above-mentioned methyl fuoride goods or methylene fluoride goods.
That is, the present invention for example, contains the content that following [1]～[19] illustrate.
[1] a kind of manufacture method of hydrogen fluorohydrocarbon, it is characterized in that containing and make methyl halide mixture and hydrogen fluoride, in gas phase, in the presence of fluorination catalyst, in single reaction zone, react, after carrying out separation and purification in the gas importing distillation tower that generates, obtain the operation of the hydrogen fluorohydrocarbon more than 2 kinds or 2 kinds.
[2] manufacture method of above-mentioned [1] described hydrogen fluorohydrocarbon is characterized in that comprising at least 2 kinds the compound that is selected from methyl chloride, methylene dichloride, trichloromethane, dichlorofluoromethane, chlorofluoromethane and the chlorodifluoromethane as the methyl halide mixture of raw material.
[3] manufacture method of above-mentioned [1] or [2] described hydrogen fluorohydrocarbon is characterized in that the methyl halide mixture is made up of methyl chloride and methylene dichloride.
[4] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[3] is characterized in that the hydrogen fluorohydrocarbon that obtains is at least 2 kinds the compound that is selected from methyl fuoride, methylene fluoride and the trifluoromethane.
[5] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[4] is characterized in that the hydrogen fluorohydrocarbon that obtains is methyl fuoride and methylene fluoride.
[6] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[5], the concentration that it is characterized in that a kind of methyl halide containing in the methyl halide mixture is in the scope of 5～95% quality.
[7] manufacture method of above-mentioned [6] described hydrogen fluorohydrocarbon, the concentration that it is characterized in that a kind of methyl halide containing in the methyl halide mixture is in the scope of 10～90% quality.
[8] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[7], it is characterized in that reacting is to carry out in the mol ratio as the hydrogen fluoride of reaction raw materials and methyl halide is 5～30 scope.
[9] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[8], it is characterized in that reacting is to carry out in 150～350 ℃ temperature range.
[10] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[9], it is characterized in that reacting is to carry out in the pressure range of 0.05～1Mpa.
[11] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[10] is characterized in that fluorination catalyst is that chromic oxide with 3 valencys is the loaded or block type catalyzer of principal constituent.
[12] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[11], it is characterized in that the gas that will generate in the single reaction band imports the 1st distillation tower, mainly isolate hydrogenchloride and hydrogen fluorohydrocarbon from cat head, at the bottom of tower, mainly isolate hydrogen fluoride and unreacted methyl halide.
[13] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[12], it is characterized in that and to import the 2nd distillation tower from main isolated hydrogenchloride of the cat head of the 1st distillation tower and hydrogen fluorohydrocarbon, mainly isolate hydrogenchloride from cat head, at the bottom of tower, mainly isolate the hydrogen fluorohydrocarbon, the hydrogen fluorohydrocarbon is carried out separation and purification and reclaim as goods.
[14] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[13] is characterized in that main isolated hydrogen fluoride and unreacted methyl halide at the bottom of the tower of the 1st distillation tower are circulated to the single reaction band of reaction process.
[15] manufacture method of each described hydrogen fluorohydrocarbon of above-mentioned [1]～[14], the working pressure that it is characterized in that the 1st distillation tower and the 2nd distillation tower is in the scope of 0.3～3Mpa.
[16] a kind of methyl fuoride goods, the purity that it is characterized in that containing each described manufacture method acquisition of using above-mentioned [1]～[15] is the methyl fuoride more than or equal to 99.999% volume.
[17] a kind of methylene fluoride goods is characterized in that, the purity that contains each described manufacture method acquisition of using above-mentioned [1]～[15] is the methylene fluoride more than or equal to 99.999% volume.
[18] a kind of etching gas or purge gas is characterized in that containing above-mentioned [16] described methyl fuoride goods.
[19] a kind of etching gas or purge gas is characterized in that containing above-mentioned [17] described methylene fluoride goods.
According to the present invention, can be industrial advantageously make and can be in production process of semiconductor device use highly purified hydrogen fluorohydrocarbon class, particularly methyl fuoride, methylene fluoride as etching gas or purge gas.
The simple declaration of accompanying drawing
Fig. 1 is the synoptic diagram that is illustrated in an example of the device that uses in the manufacture method of hydrogen fluorohydrocarbon of the present invention.
The invention embodiment
Below, the manufacture method of hydrogen fluorohydrocarbon of the present invention, its goods and uses thereof are elaborated.
As the manufacture method of methyl fuoride, as described above known, various methods are arranged all the time.Wherein, make methyl alcohol and hydrogen fluoride in gas phase, carry out fluorizated method, (2) react methyl chloride and hydrogen fluoride in gas phase method in the presence of the fluorination catalyst in the presence of the chromium fluoride catalyzer for (1), the method of use methyl alcohol (1), existence is because of the corrosion that generates the device materials that water caused or select the problem of rate variance etc., the method of use methyl chloride (2), exist in and have balance in the reaction, the low problem that waits of yield.On the other hand, as the manufacture method of methylene fluoride, known have (3) to make hydrogen fluoride and methylene dichloride or chlorofluoromethane, the method for in gas phase or liquid phase, reacting, but it is to be solved to also have many problems to have as inexpensive method of manufacturing economically.
In addition, manufacture method as the hydrogen fluorohydrocarbon more than 2 kinds or 2 kinds, as mentioned above, knownly making 1,1 with two reactors, 1, in the operation of 2-Tetrafluoroethane, add methyl chloride, trieline, and the method for reacting, but these methods all have two different reaction zones of reaction conditions (first reactor and second reactor), also have problem to be solved as inexpensive method of manufacturing economically.
Below, the optimal way of the manufacture method of hydrogen fluorohydrocarbon of the present invention is elaborated.
The manufacture method of hydrogen fluorohydrocarbon of the present invention, be characterised in that and comprise as raw material use methyl halide mixture and hydrogen fluoride, make their (reactor) reactions in single reaction zone in the presence of fluorination catalyst in gas phase, after carrying out separation and purification in the gas importing distillation tower that generates, obtain the operation of the hydrogen fluorohydrocarbon more than 2 kinds or 2 kinds.As the methyl halide mixture of raw material, preferably comprise and be selected from methyl chloride (CH
3Cl), methylene dichloride (CH
2Cl
2), trichloromethane (CHCl
3), dichlorofluoromethane (CHCl
2F), chlorofluoromethane (CH
2ClF) and chlorodifluoromethane (CHClF
2) at least 2 kinds compound, more preferably comprise methyl chloride and methylene dichloride.As the supply method of these raw materials, can select to supply with respectively separately, in reactor inlet place blended method or from beginning any with the method for admixture supply just.In addition, the methyl halide mixture, preferably in the leading portion of supplying with in reactor, for example, the dewatering agent of use molecular sieve etc. is removed moisture content or is removed destabilizing agent etc.
The concentration of the a kind of methyl halide that contains in the methyl halide mixture, preferably in the scope of 5～95 quality %, more preferably in the scope of 10～90 quality %, as long as in this concentration range, for example, just can obtain to adjust arbitrarily the advantage of necessary turnout.Methyl halide and hydrogen fluoride as starting raw material are mixed at the reactor inlet place.The mol ratio of hydrogen fluoride and methyl halide (supply ratio) is preferred 5～30, and is big less than the generation ratio of 5 o'clock impurities, the selection rate variation.In addition, if surpass 30, then yield reduces, and the circulation quantitative change of unreacting material or intermediate is many, and it is big that device becomes, and is not preferred therefore.The methyl halide mixture and the hydrogen fluoride of raw material, the place is mixed at reactor inlet, after the preheater heating, is directed in the single reaction band (reactor).From preventing the preferred multitube of viewpoint starting reaction device of bias current.The fluorination catalyst that is filled in reactor is a principal constituent with the chromic oxide of 3 valencys preferably, the catalyzer of loaded or block type.As the preferred aluminum oxide of the carrier of supported catalyst, fluorided alumina, gac etc.In addition, except that the chromic oxide of 3 valencys, can also contain a spot of interpolation metal, as adding the preferred indium of metal, nickel, zinc and/or cobalt.These fluorination catalysts, preferably at the leading portion of reaction, for example, at least a portion is by the hydrogen fluoride fluorizated.Preferred 150～350 ℃ of range of reaction temperature, more preferably 200～300 ℃.Reaction yield reduces when being lower than 150 ℃, and not preferred, increases sometimes if surpass 350 ℃ then undesirable impurity.The pressure range of reaction is preferably 0.05～1.0Mpa, more preferably 0.1～0.7Mpa.Operational difficulty when being lower than 0.05Mpa if surpass 1.0Mpa then must select more withstand voltage structure etc., is uneconomic.To in reactor, react at least a portion of generation (outlet) gas that is generated, for example, cool off, and import in the 1st distillation tower with pump, or import in the 1st distillation tower with compressor.The working pressure of the 1st distillation tower, from the viewpoint of economy, operability, preferred 0.3～3Mpa.In (a) of distillation mode, be directed to the generation gas in the 1st distillation tower, mainly isolate hydrogenchloride, hydrogen fluorohydrocarbon from cat head, and import the gas of the 2nd distillation tower, mainly isolate unreacted hydrogen fluoride, unreacted methyl halide at the bottom of the tower of the 1st distillation tower, this is recycled in the single reaction band as reaction process.Import main hydrogenchloride, hydrogen fluorohydrocarbon in the 2nd distillation tower, in working pressure is the pressure range of 0.3～3Mpa, mainly isolate hydrogenchloride, and hydrogenchloride for example, can be used for other purposes by it is absorbed in the water from cat head.The hydrogen fluorohydrocarbon that is contained at least a portion in the hydrogenchloride can be recovered, and utilizes again.Mainly isolate the hydrogen fluorohydrocarbon at the bottom of the tower of the 2nd distillation tower, it is imported in the 3rd distillation tower, isolate low boilers from cat head in working pressure is the pressure range of 0.3～3Mpa, for example, methyl fuoride is reclaimed as goods by refining back in refining step.In addition, isolate high boiling product at the bottom of tower, for example, methylene fluoride is reclaimed as goods by refining back in refining step.In (b) of distillation mode, be directed to the generation gas in the 1st distillation tower, mainly isolate hydrogenchloride from cat head, reclaim equally with (a), utilize again.At the bottom of tower, mainly isolate unreacted hydrogen fluoride, unreacted methyl halide, hydrogen fluorohydrocarbon, they are imported in the 2nd distillation tower, in the 2nd distillation tower, mainly isolate the hydrogen fluorohydrocarbon, it is imported in the 3rd distillation tower from cat head.At the bottom of the tower of the 2nd distillation tower, mainly isolate unreacted hydrogen fluoride, unreacted methyl halide, they are utilized with (a) being circulated in the reaction process equally.Be imported into the main hydrogen fluorohydrocarbon in the 3rd distillation tower, isolate low boilers from cat head, for example, methyl fuoride by refining, reclaims as goods in refining step.In addition, isolate high boiling product at the bottom of tower, for example, methylene fluoride by refining, reclaims as goods in refining step.
Distillation mode (a) and (b) in, all be from the isolated low-boiling-point substance of the cat head of the 3rd distillation tower, for example, methyl fuoride, isolated high boiling material at the bottom of the tower, for example, methylene fluoride, can in refining step, remove, utilize the adsorption treatment (molecular sieve and/or gac) of sorbent material etc., and obtain the high-purity product of purity more than or equal to 99.999% volume through inert substance (oxygen, nitrogen etc.).Purity is more than or equal to 99.999% volume, for example, methyl fuoride or methylene fluoride can use TCD method, FID method (any all contains the precut method), ECD method or the gas chromatography combined with mass spectrometry analyser analysis instruments such as (GC-MS) of vapor-phase chromatography (GC) to analyze.
Then, the hydrogen fluorohydrocarbon, particularly methyl fuoride that uses manufacture method of the present invention to obtain, the purposes of methylene fluoride are described.Highly purified methyl fuoride, methylene fluoride or with He, N
2, Ar etc. rare gas element, O
2, NF
3Deng the mixed gas of gas (in this manual, be collectively referred to as " methyl fuoride goods ", " methylene fluoride goods "), can be used as the etching gas in the etching work procedure in the process for fabrication of semiconductor device or use as the purge gas in the process for fabrication of semiconductor device.Engraving method can carry out under various dry etching conditions such as plasma etching, microwave etching, also can be in the proper ratio and He, N
2, rare gas element or HCl, O such as Ar
2, H
2, F
2, NF
3Mix use Deng gas.
Below, illustrate in greater detail the present invention by embodiment, and the present invention is not limited only to these embodiment.
Embodiment 1
Preparation of catalysts example 1
To in 10 liters container, add 0.6 liter of pure water, stirring, and in this pure water about 1 hour of time spent drip and in 1.2 liters of pure water, dissolved 452g Cr (NO
3) 9H
2O and 42g In (NO
3)
3NH
2The solution of O (n is about 5) and 0.31 liter of 28% ammoniacal liquor, the flow of two kinds of aqueous solution of control is so that the pH of reaction solution becomes in 7.5～8.5 scope.The slurry that filter to obtain, with the solid substance that filters out with the pure water thorough washing after, 120 ℃ dry 12 hours down.After the pulverizing of exsiccant solid substance, mix with graphite, utilize the granulating and forming device to make particle.This particle under nitrogen gas stream, was burnt till 4 hours at 400 ℃, make catalyst precursor.Then, catalyst precursor is filled in the tophet system reactor, at first under normal pressure, 350 ℃, under the flow of hydrogen fluoride of nitrogen dilution, carries out fluoridation (activation of catalyzer).Then, under the pressure of 0.3Mpa, further under the flow of hydrogen fluoride of nitrogen dilution, then under 100% flow of hydrogen fluoride, carry out fluoridation (activation of catalyzer), make catalyzer.
Embodiment 2
The modulation example 2 of catalyzer
With 191.5g chromium chloride (CrCl
36H
2O) put in 132 ml pure waters, be heated to 70～80 ℃ with water-bath and dissolve.After solution was cooled to room temperature, dipping 400g activated alumina (day is waved ユ ニ バ one サ Le (strain) NST-7) all was absorbed in the aluminum oxide above-mentioned solution.
Then, the aluminum oxide of moisture state is dry in 90 ℃ water-bath, carry out dry solidification.The catalyzer of dry solidification is following dry 3 hours at 110 ℃ in the hot-air drier of air cycle type.The exsiccant catalyzer is filled in the SUS container made, with space velocity (SV) 540Hr
-1Come ventilating air, under circulation, burn till.Burn till to the heating disappearance of catalyst layer at 200 ℃, further be warming up to 400 ℃, burn till and obtained catalyzer in 3 hours.This catalyzer is filled in the tophet system reactor, at first under normal pressure, 250 ℃, under the flow of hydrogen fluoride of nitrogen dilution, further heat up gradually, carry out fluoridation, then at 350 ℃, under the pressure of 0.3Mpa, further under the flow of hydrogen fluoride of nitrogen dilution, then under 100% flow of hydrogen fluoride, carry out fluoridation, make catalyzer.
Embodiment 3
The manufacturing of hydrogen fluorohydrocarbon
In the tophet 600 type reactors of 1 inch of internal diameter, long 1m, 100 milliliters of the catalyzer that obtains among the filling embodiment 1 in the time of circulation nitrogen, make the temperature of reactor remain on 300 ℃, and pressure remains on 0.2Mpa.
Then, with 82 standard liters/hour flow velocity supply with hydrogen fluoride, stop the supply of nitrogen then.From a material-guiding inlet, with 3 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methyl chloride (CH after the processed
3Cl), from another material-guiding inlet, with 1 standard liter/hour supply with zeolite (molecular sieve: 3A) carry out methylene dichloride (CH after the processed
2Cl
2), begin reaction.After 2 hours, the exit gas of reactor removed acidic components with the potassium hydroxide aqueous solution washing after, find to have the following composition that illustrates (unit: the % volume) when analyzing with gas chromatograph.
CH
3F 13.3253 CH
2F
2 24.6108
CH
2ClF 0.3720 CH
2Cl
2 0.0205
CH
3Cl 61.6557 other 0.0157
Embodiment 4
The manufacture method of hydrogen fluorohydrocarbon
Similarly to Example 3, in the tophet 600 type reactors of 1 inch of internal diameter, 1 meter of length, 100 milliliters of the catalyzer that obtains among the filling embodiment 1 in the time of circulation nitrogen, remain on 300 ℃ with temperature of reactor, and pressure remains on 0.2Mpa.
Then, with 82 standard liters/hour flow velocity supply with hydrogen fluoride, stop the supply of nitrogen then.From a material-guiding inlet, with 2 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methyl chloride (CH after the processed
3Cl), from another material-guiding inlet, with 2 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methylene dichloride (CH after the processed
2Cl
2), begin reaction.After 2 hours, with the exit gas of reactor with potassium hydroxide aqueous solution wash remove acidic components after, come the composition of analytical gas with gas chromatograph, the result has the following composition that illustrates (unit: the % volume).
CH
3F 8.8892 CH
2F
2 49.1216
CH
2ClF?0.7210 CH
2Cl
2?0.1374
CH
3Cl 41.0983 other 0.0325
Embodiment 5
The manufacture method of hydrogen fluorohydrocarbon
In the tophet 600 type reactors of 1 inch of internal diameter, 1 meter of length, 100 milliliters of the catalyzer that obtains among the filling embodiment 1 in the time of circulation nitrogen, make temperature of reactor remain on 290 ℃, and pressure remains on 0.2Mpa.
Then, with 73.85 standard liters/hour flow velocity supply with hydrogen fluoride, stop the supply of nitrogen then.From a material-guiding inlet, with 2 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methyl chloride (CH after the processed
3Cl), from another material-guiding inlet, with 2 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methylene dichloride (CH after the processed
2Cl
2), begin reaction.After 2 hours, with the exit gas of reactor with potassium hydroxide aqueous solution wash remove acidic components after, come the composition of analytical gas with gas chromatograph, the result has the following composition that illustrates (unit: the % volume).
CH
2F
2 47.6317 CHF
3 49.0118
CH
2ClF 1.7578 CHClF
2 0.8808
CHCl
2F 0.0631 CH
2Cl
2 0.5924
CHCl
30.0321 other are 0.0303 years old
Embodiment 6
The manufacture method of hydrogen fluorohydrocarbon
In the tophet 600 type reactors of 1 inch of internal diameter, 1 meter of length, 100 milliliters of the catalyzer that obtains among the filling embodiment 1 in the time of circulation nitrogen, make temperature of reactor remain on 315 ℃, and pressure remains on 0.2Mpa.
Then, with 73.85 standard liters/hour flow velocity supply with hydrogen fluoride, stop the supply of nitrogen then.From a material-guiding inlet, with 2 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methyl chloride (CH after the processed
3Cl), from another material-guiding inlet, with 2 standard liters/hour supply with zeolite (molecular sieve: 3A) carry out methylene dichloride (CH after the processed
2Cl
2), begin reaction.After 2 hours, the exit gas of reactor removed acidic components with the potassium hydroxide aqueous solution washing after, come the composition of analytical gas with gas chromatograph, the result has the following composition that illustrates (unit: the % volume).
CH
3F 9.4268 CHF
3 49.3833
CHClF
2 0.4712 CHCl
2F 0.1176
CH
3Cl 40.5561 CHCl
3 0.0108
Other are 0.0342 years old
Embodiment 7
Highly purified CH
3The F goods
Use device shown in Figure 1, import in the 1st distillation tower reacting the reactor outlet gas that is obtained similarly to Example 3, isolate hydrogenchloride and hydrogen fluorohydrocarbon from cat head, will import from isolated hydrogen fluorohydrocarbon at the bottom of the tower of the 2nd distillation tower then and carry out separation and purification the 3rd distillation tower.In addition, in Fig. 1,1 is reactor (single reaction band), and 2 is the 1st distillation tower, and 3 is the 2nd distillation tower, and 4 is the 3rd distillation tower, and 5 is hydrogen fluorohydrocarbon refining step, and 6 is the methylene fluoride refining step.
The cat head of the 3rd distillation tower 4 shown in Figure 1 is distillated composition, analyze with TCD method, FID method and the gas chromatography combined with mass spectrometry analyser (GC-MS) of vapor-phase chromatography (GC), the result has the following composition that illustrates (unit: the % volume).
CH
3F 99.9984 CH
4 0.0005
CH
2＝CH
2 0.0005 CO
2 0.0003
Other are 0.0003 years old
To volume be fill in 100 milliliters the stainless steel cylinder 20g zeolite (molecular sieve 3a (and clear and (strain) system of ユ ニ オ Application: average fine pore 3 ) and molecular sieve 4A (ユ ニ オ Application clear and (strain) makes: equal amount of mixture average fine pore 3.5 )), after the vacuum-drying, in cooling drum, fill the above-mentioned overhead product of about 50g, maintain the temperature at-10C, the stirring that does not stop simultaneously, after about 5 hours, TCD method with vapor-phase chromatography, FID method and gas chromatography combined with mass spectrometry analyser are analyzed liquid phase part, and the result has the following composition that illustrates (unit: the % volume).
CH
3F 99.9993 CH4 ＜0.0001
CH
2＝CH
2 0.0002 CO
2 0.0002
Other are 0.0002 years old
Embodiment 8
Highly purified CH
2F
2Goods
Distillate composition at the bottom of the tower with the 3rd distillation tower 4 of embodiment 7, analyze with TCD method, FID method and the gas chromatography combined with mass spectrometry analyser (GC-MS) of vapor-phase chromatography (GC), the result has the following composition that illustrates (unit: the % volume).
CH
2F
2 99.9986 CH3Cl 0.0007
CH
2ClF 0.0005 other 0.0002
To volume is to fill in 100 milliliters the stainless steel cylinder to be mixed with 15g zeolite (molecular sieve 3a) and 5g carbonaceous adsorbent (carbonaceous molecular sieve, military field pharmacy (strain) are made: mixture average fine pore 4 ), after the vacuum-drying, in cooling drum, fill the above-mentioned overhead product of about 50g, maintain the temperature at-10 ℃, the stirring that does not stop simultaneously, after about 5 hours, TCD method, FID method and gas chromatography combined with mass spectrometry analyser with vapor-phase chromatography are analyzed liquid phase part, and the result has the following composition that illustrates (unit: the % volume).
CH
2F
2 99.9996 CH
3Cl 0.0002
CH
2ClF 0.0001 other 0.0001
Industrial utilizability
The present invention can advantageously be used in and can be used as etching gas in the manufacturing process of semiconductor devices Highly purified hydrogen fluorohydrocarbon class, the particularly fluomethane that body or purge gas use, the worker of difluoromethane Industry is made.
Claims (11)
1. the manufacture method of a hydrogen fluorohydrocarbon, it is characterized in that containing and make methyl halide mixture and the hydrogen fluoride of forming by methyl chloride and methylene dichloride, in gas phase, in the presence of fluorination catalyst, in single reaction zone, react, after carrying out separation and purification in the gas importing distillation tower that generates, obtain the operation of methyl fuoride and methylene fluoride.
2. the manufacture method of the described hydrogen fluorohydrocarbon of claim 1, the concentration that it is characterized in that a kind of methyl halide containing in the methyl halide mixture is in the scope of 5～95% quality.
3. the manufacture method of the described hydrogen fluorohydrocarbon of claim 2, the concentration that it is characterized in that a kind of methyl halide containing in the methyl halide mixture is in the scope of 10～90% quality.
4. the manufacture method of the described hydrogen fluorohydrocarbon of claim 1, it is characterized in that reacting is to carry out in the mol ratio as the hydrogen fluoride of reaction raw materials and methyl halide is 5～30 scope.
5. the manufacture method of the described hydrogen fluorohydrocarbon of claim 1, it is characterized in that reacting is to carry out in 150～350 ℃ temperature range.
6. the manufacture method of the described hydrogen fluorohydrocarbon of claim 1, it is characterized in that reacting is to carry out in the pressure range of 0.05～1Mpa.
7. the manufacture method of the described hydrogen fluorohydrocarbon of claim 1 is characterized in that fluorination catalyst is that chromic oxide with 3 valencys is the loaded or block type catalyzer of principal constituent.
8. the manufacture method of the described hydrogen fluorohydrocarbon of claim 1 is characterized in that the gas that will generate in the single reaction band imports the 1st distillation tower, mainly isolates hydrogenchloride and hydrogen fluorohydrocarbon from cat head, mainly isolates hydrogen fluoride and unreacted methyl halide at the bottom of tower.
9. the manufacture method of the described hydrogen fluorohydrocarbon of claim 8, it is characterized in that and to import the 2nd distillation tower from main isolated hydrogenchloride of the cat head of the 1st distillation tower and hydrogen fluorohydrocarbon, mainly isolate hydrogenchloride from cat head, at the bottom of tower, mainly isolate the hydrogen fluorohydrocarbon, the hydrogen fluorohydrocarbon is carried out separation and purification and reclaim as goods.
10. the manufacture method of the described hydrogen fluorohydrocarbon of claim 8 is characterized in that main isolated hydrogen fluoride and unreacted methyl halide at the bottom of the tower of the 1st distillation tower are circulated to the single reaction band of reaction process.
11. the manufacture method of the described hydrogen fluorohydrocarbon of claim 9, the working pressure that it is characterized in that the 1st distillation tower and the 2nd distillation tower is in the scope of 0.3～3Mpa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP318556/2003 | 2003-09-10 | ||
| JP2003318556 | 2003-09-10 |
Publications (2)
| Publication Number | Publication Date |
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| CN1701056A CN1701056A (en) | 2005-11-23 |
| CN1330615C true CN1330615C (en) | 2007-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800012200A Active CN1330615C (en) | 2003-09-10 | 2004-09-09 | Process for production of hydrofluorocarbons, products thereof and use of the products |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4785532B2 (en) |
| KR (1) | KR100643674B1 (en) |
| CN (1) | CN1330615C (en) |
| TW (1) | TW200516068A (en) |
| WO (1) | WO2005026090A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2901790A1 (en) * | 2006-05-30 | 2007-12-07 | Arkema France | PROCESS FOR PRODUCING HYDROFLUOROCARBONS |
| WO2011102268A1 (en) * | 2010-02-17 | 2011-08-25 | セントラル硝子株式会社 | Method for producing semiconductor gas |
| JP5652179B2 (en) * | 2010-12-09 | 2015-01-14 | セントラル硝子株式会社 | Method for producing semiconductor gas |
| CN103910600A (en) * | 2013-01-06 | 2014-07-09 | 中化蓝天集团有限公司 | Method for preparing ultrapure fluoromethane |
| JP2014221727A (en) * | 2013-05-13 | 2014-11-27 | 昭和電工株式会社 | Dichloromethane purification method and method of producing difluoromethane using the same |
| JP6261531B2 (en) * | 2015-02-05 | 2018-01-17 | ダイキン工業株式会社 | Method for producing methyl fluoride |
| CN109748775B (en) * | 2017-11-08 | 2021-08-17 | 浙江蓝天环保高科技股份有限公司 | Resource utilization method of by-product trifluoromethane in HCFC-22 production |
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2004
- 2004-09-08 TW TW093127173A patent/TW200516068A/en not_active IP Right Cessation
- 2004-09-09 KR KR1020057008285A patent/KR100643674B1/en active IP Right Grant
- 2004-09-09 JP JP2005513956A patent/JP4785532B2/en active Active
- 2004-09-09 CN CNB2004800012200A patent/CN1330615C/en active Active
- 2004-09-09 WO PCT/JP2004/013482 patent/WO2005026090A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1701056A (en) | 2005-11-23 |
| TWI325412B (en) | 2010-06-01 |
| JPWO2005026090A1 (en) | 2006-11-16 |
| KR20050086475A (en) | 2005-08-30 |
| KR100643674B1 (en) | 2006-11-10 |
| WO2005026090A1 (en) | 2005-03-24 |
| JP4785532B2 (en) | 2011-10-05 |
| TW200516068A (en) | 2005-05-16 |
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