CN1004694B - Process for the synthesis of choropentafluoroethae from dichlorotetrafluoroethane and hydrofluoric acid - Google Patents

Process for the synthesis of choropentafluoroethae from dichlorotetrafluoroethane and hydrofluoric acid Download PDF

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CN1004694B
CN1004694B CN86107751.2A CN86107751A CN1004694B CN 1004694 B CN1004694 B CN 1004694B CN 86107751 A CN86107751 A CN 86107751A CN 1004694 B CN1004694 B CN 1004694B
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hydrofluoric acid
aluminum oxide
catalyzer
pore
mixture
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CN86107751A (en
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罗贝尔·阿泽拉德
贝尔纳·谢曼纳尔
亨利·马泰斯
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Arkema France SA
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Atochem SA
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Priority claimed from FR8516951A external-priority patent/FR2590251B1/en
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract

The invention relates to a gas phase process for the manufacture of chloropentafluoroethane by the action of hydrofluoric acid on dichlorotetrafluoroethane in the presence of a catalyst, the said catalyst being prepared by reacting, in a gaseous phase, an alumina in which the sodium oxide content is below 300 ppm and the volume of the pores having a radius equal to 40 angstroms or above is greater than 0.7 cm3/g, with hydrofluoric acid or with a mixture of hydrofluoric acid and of air, nitrogen or a fluorinated compound.

Description

Method by dichloro tetrafluoro ethane and the synthetic chloropentafluoroethane of hydrofluoric acid
The invention relates to dichloro tetrafluoro ethane C 2F 4Cl 2Pass through gas phase catalytic reaction with hydrofluoric acid, generate chloropentafluoroethane C 2F 5The preparation method of Cl.
Chloropentafluoroethane can be used as solvent, propelling agent or refrigerating fulid.It can be produced by various known methods, and for example, by tetrachloroethylene, chlorine and hydrofluoric acid are produced (No. 117,580, Deutsches Wirtschafts Patent), perhaps in the presence of aluminum trifluoride, by Refrigerant R 113 C 2F 3Cl 2Gas-phase reaction preparation (Japanese patent application publication No. 48-26,729/73) with hydrofluoric acid.
United States Patent (USP) 3,087, the vapour phase disproportionation reaction of having narrated the chlorine fluorine compound on catalyzer for No. 974 is without hydrofluoric acid.The disproportionation reaction of dichloro tetrafluoro ethane is then undertaken by following formula:
2C 2Cl 2F 4→C 2ClF 5+C 2Cl 3F 3
This catalyzer is the activated alumina of high surface area, before being used for disproportionation reaction, must handle with fluorocarbon earlier.CF 2ClCF 2Cl is converted into C 2ClF 5Transformation efficiency, be no more than the 34%(mole), and most C 2Cl 3F 3Then produce as paying product.
United States Patent (USP) 3,258,500 have narrated the fluoridation of carrying out vapor phase catalytic with hydrofluoric acid.Dichloro tetrafluoro ethane CF 2Cl-CF 2Cl and hydrofluoric acid HF are with (HF/CF 2Cl-CF 2Cl) is 4 to 5 molar ratio,, on the oxide catalyst of chromium, reacts in 400 ℃.The hexafluoroethane C that is generated 2F 6With respect to C 2F 5The mol ratio of Cl is 0.19.
People's such as L.Marangoni paper " is produced chloropentafluoroethane by dichloro tetrafluoro ethane " (fluorochemical The Chemicals, 1981/82 year, the 19th phase, 21 pages to 34 pages), also narrates, and will be that the catalyzer of basal component is used for by C with the chromated oxide 2F 4Cl 2With HF vapor phase production C 2F 5The reaction of Cl.C 2F 4Cl 2Transformation efficiency be 72-75%, C 2F 5The productive rate of Cl is 89～92%, and the generation of hexafluoroethane remains C 2F 5The 8%(mole of Cl resultant).
People's such as M.Vecchio paper, " research for preparing the chlorine fluoroethane about vapor-phase process " (fluorochemical The Chemicals, 1974, the 4th phase, 111 pages to 139 pages), also narrated the reaction same with above-mentioned paper, just catalyzer is to add with nickel, iron and hafnium halide on the basal component aluminum fluoride.C 2F 4Cl 2Transformation efficiency be no more than 41%, and C 2F 5Cl is 38% in the molecular fraction of reactor outlet.
The catalyzer of prior art is difficult to preparation, and is used for C 2F 5The productive rate of Cl and selectivity all are medium levels.
The present invention overcomes all above-mentioned shortcomings, for producing C 2F 5Cl provides simple, a flexible and economic method.
According to method of the present invention, its main points are, make dichloro tetrafluoro ethane C 2Cl 2F 4In the presence of catalyzer, in gas phase, be subjected to the effect of hydrofluoric acid HF.Catalyzer then is by activated alumina and hydrofluoric acid, or with hydrofluoric acid and air, nitrogen or and the mixture of a kind of compound of fluorine, in gas phase, react and make.In the activated alumina, the content of sodium oxide is less than 300ppm, and radius is equal to and greater than its volume of pore of 40 dusts then greater than 0.7 centimetre 3/ gram.
Obtain thus up to the starting material transformation efficiency more than 80%, and C 2F 5The high yield of Cl.Another advantage of this method is that life of catalyst is long.
The preparation of activated alumina is by temperature control heated oxide aluminium hydrate, so that remove the big water gaging (Kirk-Othmer, chemical technology encyclopaedia, the 3rd edition, the 2nd volume, 225 pages) in the resultant.
The aluminum oxide that is used to produce catalyzer is commercially availabie aluminum oxide.As long as select radius to be equal to and greater than the pore volume of 40 dusts greater than 0.7 centimetre 3/ gram is preferably in 0.75 and 1 centimetre 3Activated alumina between the/gram just can.Concerning aluminum oxide, make diameter less than 20 millimeters, be preferably less than several millimeters granular, little pearl or extrusion type can help the handled easily of reactor in reinforced and discharge process.
As mentioned above, Na 2O content must be less than 300ppm, and preferably as far as possible little.And select a kind of silicon oxide-containing to be not more than 0.5%(weight), ferric oxide F 2O 3Be not more than 0.2%(weight) aluminum oxide be favourable.This aluminum oxide by it and HF reaction, perhaps with the mixture reaction of a kind of compound of HF and air, nitrogen or fluorine, is converted into aluminum trifluoride AlF 3Mixture with aluminum oxide.
For example, can use dichloro tetrafluoro ethane C 2Cl 2F 4With the mixture of hydrofluoric acid, under enough temperature, on aluminum oxide, pass through, be converted into the reaction of aluminum trifluoride to impel aluminum oxide.More suitable between operating between 150 ℃ to 500 ℃.Preferably under atmospheric pressure, operate in 5 to 15 seconds duration of contact.The expert can carry out this reaction easily, and regulates C 2F 4Cl 2With the proportioning of HF, temperature, pressure and duration of contact, in case oxidation aluminium damages because of the exothermicity of reacting is subjected to high temperature.
After if reactant gases passes through, when gaseous constituent no longer changes, mean that then aluminum oxide has been converted into catalyzer on aluminum oxide.After washing with water, suitable, just can be applicable to C 2F 4Cl 2Fluoridize and be C of the present invention 2F 5Work among the Cl.
According to most preferred embodiment of the present invention, catalyzer also can make aluminum oxide at thermopnore, contained hydrofluoric acid hot blast effect and prepare.Service temperature is more suitable between 150 and 500 ℃.HF and AIR MIXTURES then 0.1 and the 30%(mole) between, help between being preferably in 1.5 and 3% using.Favourable flow is 200～250 moles/hour and rises catalyzer.Operation being preferably in normal atmosphere, carries out under 350 ℃ or the above temperature.Changing the aerial concentration of HF, is easily with control reaction liberated heat.When not having more HF to be consumed, just make reaction terminating, this catalyzer then can be regarded as and can be used for C at any time 2F 4Cl 2Transformation.
Dichloro tetrafluoro ethane C 2F 4Cl 2With the reaction of anhydrous hydrofluoric acid HF be in gas phase, to carry out by catalyzer, this catalyzer can prepare according in last two methods any one.Temperature 350～550 ℃ favourable, preferably between 380 and 500 ℃.HF/C 2Cl 4F 2Molar ratio be that 0.5-1.5 is favourable, be preferably between 0.9 and 1.1.Though reaction can be carried out under any pressure, as long as it remains in gas phase, and operation is the most convenient under 0.5～4 crust absolute pressure, however, had better be at the close pressure of normal atmosphere, 5～15 seconds duration of contact are preferably between 6 seconds and 13 seconds.
The following examples are used to illustrate the present invention, rather than restriction the present invention.
Used C among all these embodiment 2F 4Cl 2All contain 92.7% symmetric isomer.
Embodiment 1
The pure activated alumina (belonging to Al4192) that adopts Kaiser company to provide, adopt 0.8 millimeter/(1/32 ") extrusion type, its characteristics are as follows:
Pore radius is more than or equal to 40 dusts
Pore volume=0.91 centimetre of pore 3/ gram
Total specific surface (BET)=161 meter 2/ gram
Average pore radius=106 dusts
Apparent density (volume that compresses)=0.47
Pore radius is 50 and 250 dusts
Between surface-area=105 meter in hole 2/ gram
Fe 2O 3Content 0.08%(weight)
SiO 2Content 0.13%(weight)
Na 2O content 0.015%(weight)
With 0.12 liter in this aluminum oxide, be incorporated in the tubular reactor of 28 millimeters of internal diameters with a fixed bed, the condition of according to the form below is converted into catalyzer with aluminum oxide then.
The absolute pressure reactant rubs time duration of contact in the reactor
Your flow (second) (accumulative hours) of temperature ℃ (normal atmosphere)
Mole/hour
* 100 milliliters
Catalyzer)
C 2Cl 2F 4HF
350 1 0.374 0.177 12.8 48
380 1 0.328 0.178 12.7 93
410 1 0.337 0.187 12.2 142
When above-mentioned processing ending, oxygen-free acid water and wash with aqueous sodium hydroxide washes after, leave in the gas of reactor C 2ClF 5Ratio reach 23.6%, and it only has 0.7% in the time of 350 ℃.
Temperature of reactor is risen to 450 ℃ then, C 2Cl 2F 4Quality the same.Its result is shown in the following table 1.Molar flow in the table be illustrated in reactor pressure be absolute pressure be 1 the crust, temperature remains in 450 ℃, reactant is by the amount of per 0.1 liter of catalyzer.The catalyzer working hour shown in the table comprises that aluminum oxide is converted into giving the stage fully of catalyzer.
In all above-mentioned tests, unconverted dichloro tetrafluoro ethane (is about used C 2Cl 2F 415% mole of compound) contains 20～25% symmetric isomer C F 2Cl-CF 2Cl.
Operate after 550 hours, under the above-mentioned working conditions with pure air under 450 ℃ of regenerated conditions, the result that catalyzer produces is with top definitely identical.
Implement 2
Adopt the activated alumina identical with embodiment 1, and get identical profile, promptly 0.8 millimeter extrusion type leans on fluidization that it is converted to catalyzer simultaneously.Get 0.125 liter in Kaiser4192 type aluminum oxide, promptly 51.3 grams are heated to 350 ℃ in nitrogen gas stream, then, under atmospheric pressure, the gas mixture below importing 24 hours.
Air ... 27.2 mole/time
HF ... 0.77 mole/time
After this handled 24 hours, catalyzer contained 62% fluorine, in other words, contains 91.4% aluminum fluoride and 8.6% unconverted aluminum oxide.The weight of catalyzer increases to 77.9 grams.
Get this catalyzer 68.1 grams (0.1 liter), in the tubular reactor of 28 millimeters of similarly to Example 1 diameters, test according to the step of embodiment 1.The results are shown in the following table II.
The listed catalyzer working hour, its cycle originates in fixed bed reinforced to reactor, but does not comprise that aluminum oxide is converted into the time of catalyzer.
Embodiment 3
According to the method for embodiment 2, begin with same activated alumina, only after aluminum oxide is converted into catalyzer, it is added reactor with fixed bed, so that C 2F 4Cl 2Carry out fluoridation.Reaction is with HF/C 2Cl 2F 4Molar ratio near 1 beginning, rather than 0.4 among the embodiment 2.
It the results are shown in the table III.
The method that begins does not so change activity of such catalysts and selectivity.
Working hour in the table, its cycle is to start from fixed bed to feed in raw material to reactor, but does not comprise that aluminum oxide is converted into the time of catalyzer.
Embodiment 4(comparative example)
According to the step operation of embodiment 2, but the pore volume of used activated alumina is with different according to activated alumina used in the method for the present invention.Used aluminum oxide is SCM250, it is characterized in that:
Chemical purity
Na 2O 800ppm
Fe 2O 3300ppm
SiO 2200ppm
Physical properties:
Form: little pearl, 2 to 4 millimeters of diameters
Specific surface (BET)=270 meter 2/ gram
Pore radius more than or equal to
The cumulative volume in the hole of 40 dusts=0.63 centimetre 3/ gram
Mean pore size: 90 dusts
Volume density: 0.66 grams per milliliter
The catalyzer of producing, wherein AlF 3Content is 87.7%(weight), the rest is unconverted aluminum oxide.The results are shown in the expression IV, in 1.The mensuration of working hour is the same with embodiment 2
Adopt same SCM250 aluminum oxide, its particle diameter is 2 to 4 millimeters, with in the past the same, it is converted into catalyzer, just, after transforming, with the method for machinery it is reduced to granule less than 1 millimeter, with size near Kaiser oxidation aluminum shot in embodiment 1,2 and 3.Then, compare catalyzer with top equally the use.
The results are shown in the table IV, 2.
Working hour shown in the table does not comprise that transforming aluminum oxide is the time of catalyzer.
Embodiment 5
The CS331-1 aluminum oxide that adopts catalyzer and pharmaceutical chemicals Europe (CCE) company to sell.
Its main physical performance is as follows:
Shape: extrusion type, diameter 1/16 " (1.6 millimeters)
Active surface area (BET): 255 meters 2/ gram
Mean pore size: 90 dusts
Pore radius more than or equal to
The pore volume of 40 dusts: 0.76 centimetre 3/ gram
Volume density: 0.60 grams per milliliter.
Na 2O 200ppm
Fe 2O 3800ppm
SiO 2300ppm
Method by embodiment 2 is produced catalyzer, AlF in the catalyzer 3Concentration to be 92%, 8% be unconverted aluminum oxide.
The results are shown in the following table V of corresponding test.Can know from the gained result and to see, be better than comparing embodiment 4(SCM250 aluminum oxide) in those results of gained.
The shown working hour does not comprise that aluminum oxide is converted into the time of catalyzer.
Embodiment 6(comparative example)
According to non-a kind of method of the present invention, fluoridize C with HF 2F 4Cl 2
Not as in the past, get aluminum oxide, and it is converted into catalyzer, but adopt a kind of industrial aluminum trifluoride powder that contains 8% left and right sides aluminum oxide.
Its main physical character is as follows:
The mean particle size of powder: 50 to 80 microns
Total specific surface (BET)=1.6 meter 2/ gram
Pore radius more than or equal to
The pore volume of the pore of 40 dusts: 0.25 centimetre 3/ gram
After this, according to fluoridizing C with HF among the top embodiment 2F 4Cl 2Step operate, just replace fixed bed with fluidized-bed.
The result comes together in the table VI.
Embodiment 7
According to the operation of the step of embodiment 2, adopt same model aluminum oxide (Kaiser4192) but with short work duration of contact.
The results are shown in the table VII, the working hour does not wherein comprise that aluminum oxide is converted into the time of catalyzer.
Find C 2ClF 5Ratio output can increase significantly, and can not damage productive rate.
The table VIII has been compiled the result who is obtained under the similar operation condition, shown Na simultaneously 2The effect of O composition.
Figure 86107751_IMG1
Figure 86107751_IMG5
Figure 86107751_IMG6
Figure 86107751_IMG7
Figure 86107751_IMG9

Claims (12)

1, a kind of vapor phase process for preparing chloropentafluoroethane, this method is in the presence of catalyzer, acting on dichloro tetrafluoro ethane with hydrofluoric acid takes place, it is characterized in that catalyzer is by activated alumina and hydrofluoric acid, or with hydrofluoric acid and air, nitrogen or and the mixture of a kind of compound of fluorine, in gas phase the reaction and make, in the activated alumina, sodium oxide content is less than 300ppm, and pore radius is equal to and greater than the pore volume of pore of 40 dusts greater than 0.7 centimetre 3/ gram.
According to the method for claim 1, it is characterized in that 2, the volume that used a kind of aluminum oxide, its pore radius are equal to and greater than the pore of 40 dusts is at 0.75 and 1 centimetre 3Between/the gram.
According to the method for claim 1, it is characterized in that 3, the purity of aluminum oxide is greater than 99.2%(weight).
4, according to the method for claim 1, it is characterized in that, aluminum oxide in pelletized form, its diameter is less than 20 millimeters.
According to the method for claim 1, it is characterized in that 5, Preparation of catalysts is the mixture with air or nitrogen and hydrofluoric acid, between 150 to 500 ℃, acts on aluminum oxide.
According to the method for claim 5, it is characterized in that 6, in the mixture of HF and air or nitrogen, HF content is 0.1 to 30%(mole) between, preferably at 1.5 to 3%(moles) between.
7, according to the method for claim 5 or 6, operation wherein is under atmospheric pressure, carries out under 350 ℃ or higher temperature.
According to the method for claim 1, it is characterized in that 8, Preparation of catalysts is the mixture with hydrofluoric acid and dichloro tetrafluoro ethane,, carry out gas-phase reaction between in 150 to 500 ℃ by aluminum oxide.
According to the method for claim 8, it is characterized in that 9, operation is under atmospheric pressure, carry out duration of contact under the condition between 5 to 15 seconds.
According to the method for claim 1, it is characterized in that 10, the fluoridation of dichloro tetrafluoro ethane and HF is to be 0.5 to 1.5 molar ratio with the HF/ dichloro tetrafluoro ethane, preferably 0.9 to 1.1, temperature is preferably carried out between 380 to 500 ℃ at 350 to 550 ℃.
According to the method for claim 10, it is characterized in that 11, operation is to carry out under the absolute pressure between 0.5 and 4 crust.
According to the method for claim 11, it is characterized in that 12, operation is under atmospheric pressure, 5 to 15 seconds duration of contact, preferably carry out under 6 to 13 seconds the condition.
CN86107751.2A 1985-11-15 1986-11-08 Process for the synthesis of choropentafluoroethae from dichlorotetrafluoroethane and hydrofluoric acid Expired CN1004694B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8516951A FR2590251B1 (en) 1985-11-15 1985-11-15 PROCESS FOR THE SYNTHESIS OF CHLOROPENTAFLUOROETHANE FROM DICHLOROTETRAFLUOROETHANE AND FLUORHYDRIC ACID
FR8516951 1985-11-15

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GR (1) GR3000043T3 (en)
IL (1) IL80528A0 (en)
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MX (1) MX163314A (en)
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CN1041804C (en) * 1995-09-13 1999-01-27 西安近代化学研究所 Fluorination catalyst for fluorinating halogenated hydrocarbon
CN105753635B (en) * 2014-12-17 2019-01-25 中化近代环保化工(西安)有限公司 A kind of production method of perfluoroethane

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KR870004926A (en) 1987-06-02
PT83749B (en) 1989-06-30
IL80528A0 (en) 1987-02-27
ZA868619B (en) 1987-07-29
TNSN86149A1 (en) 1990-01-01
DE3662518D1 (en) 1989-04-27
MX163314A (en) 1992-04-20
CN86107751A (en) 1987-05-20
DK544986D0 (en) 1986-11-14
NO864544D0 (en) 1986-11-14
PT83749A (en) 1986-12-01
NO164470C (en) 1990-10-10
NO164470B (en) 1990-07-02
NO864544L (en) 1987-05-18
DK544986A (en) 1987-05-16
IN167592B (en) 1990-11-17
FI864632A0 (en) 1986-11-14
FI83211B (en) 1991-02-28
KR890002822B1 (en) 1989-08-04

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