AU603069B2 - Creación de Inventos y Patentes con Inteligencia Artificial

AU603069B2 – Process for the synthesis of chloropentafluoroethane from dichlorotetrafluoroethane and hydrofluoric acid
– Google Patents

AU603069B2 – Process for the synthesis of chloropentafluoroethane from dichlorotetrafluoroethane and hydrofluoric acid
– Google Patents
Process for the synthesis of chloropentafluoroethane from dichlorotetrafluoroethane and hydrofluoric acid

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Publication number
AU603069B2

AU603069B2
AU65186/86A
AU6518686A
AU603069B2
AU 603069 B2
AU603069 B2
AU 603069B2
AU 65186/86 A
AU65186/86 A
AU 65186/86A
AU 6518686 A
AU6518686 A
AU 6518686A
AU 603069 B2
AU603069 B2
AU 603069B2
Authority
AU
Australia
Prior art keywords
process according
alumina
catalyst
temperature
dichlorotetrafluoroethane
Prior art date
1985-11-15
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Ceased

Application number
AU65186/86A
Other versions

AU6518686A
(en

Inventor
Robert Azerad
Bernard Cheminal
Henri Mathais
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Arkema France SA

Original Assignee
Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1985-11-15
Filing date
1986-11-14
Publication date
1990-11-08

1986-11-14
Application filed by Atochem SA
filed
Critical
Atochem SA

1987-05-21
Publication of AU6518686A
publication
Critical
patent/AU6518686A/en

1990-11-08
Application granted
granted
Critical

1990-11-08
Publication of AU603069B2
publication
Critical
patent/AU603069B2/en

2006-11-14
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

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KRHYYFGTRYWZRS-UHFFFAOYSA-N
Fluorane
Chemical compound

F
KRHYYFGTRYWZRS-UHFFFAOYSA-N
0.000
title
claims
description
67

238000000034
method
Methods

0.000
title
claims
description
37

DDMOUSALMHHKOS-UHFFFAOYSA-N
1,2-dichloro-1,1,2,2-tetrafluoroethane
Chemical compound

FC(F)(Cl)C(F)(F)Cl
DDMOUSALMHHKOS-UHFFFAOYSA-N
0.000
title
claims
description
17

229940087091
dichlorotetrafluoroethane
Drugs

0.000
title
claims
description
17

RFCAUADVODFSLZ-UHFFFAOYSA-N
1-Chloro-1,1,2,2,2-pentafluoroethane
Chemical compound

FC(F)(F)C(F)(F)Cl
RFCAUADVODFSLZ-UHFFFAOYSA-N
0.000
title
claims
description
11

239000004340
Chloropentafluoroethane
Substances

0.000
title
claims
description
11

235000019406
chloropentafluoroethane
Nutrition

0.000
title
claims
description
11

230000015572
biosynthetic process
Effects

0.000
title
description
6

238000003786
synthesis reaction
Methods

0.000
title
description
4

239000003054
catalyst
Substances

0.000
claims
description
64

PNEYBMLMFCGWSK-UHFFFAOYSA-N
aluminium oxide
Inorganic materials

[O-2].[O-2].[O-2].[Al+3].[Al+3]
PNEYBMLMFCGWSK-UHFFFAOYSA-N
0.000
claims
description
52

238000006243
chemical reaction
Methods

0.000
claims
description
35

IJGRMHOSHXDMSA-UHFFFAOYSA-N
Atomic nitrogen
Chemical compound

N#N
IJGRMHOSHXDMSA-UHFFFAOYSA-N
0.000
claims
description
20

239000011148
porous material
Substances

0.000
claims
description
14

239000000203
mixture
Substances

0.000
claims
description
12

-1
fluoro compound
Chemical class

0.000
claims
description
10

229910052757
nitrogen
Inorganic materials

0.000
claims
description
10

239000007792
gaseous phase
Substances

0.000
claims
description
9

238000003682
fluorination reaction
Methods

0.000
claims
description
7

238000004519
manufacturing process
Methods

0.000
claims
description
6

239000002253
acid
Substances

0.000
claims
description
5

KKCBUQHMOMHUOY-UHFFFAOYSA-N
sodium oxide
Chemical compound

[O-2].[Na+].[Na+]
KKCBUQHMOMHUOY-UHFFFAOYSA-N
0.000
claims
description
4

239000003570
air
Substances

0.000
claims
description
3

239000002245
particle
Substances

0.000
claims
description
3

229910001948
sodium oxide
Inorganic materials

0.000
claims
description
3

QPJSUIGXIBEQAC-UHFFFAOYSA-N
n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide
Chemical compound

CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl
QPJSUIGXIBEQAC-UHFFFAOYSA-N
0.000
description
27

KLZUFWVZNOTSEM-UHFFFAOYSA-K
Aluminium flouride
Chemical compound

F[Al](F)F
KLZUFWVZNOTSEM-UHFFFAOYSA-K
0.000
description
7

239000000460
chlorine
Substances

0.000
description
7

239000012071
phase
Substances

0.000
description
6

239000007789
gas
Substances

0.000
description
5

XEEYBQQBJWHFJM-UHFFFAOYSA-N
Iron
Chemical compound

[Fe]
XEEYBQQBJWHFJM-UHFFFAOYSA-N
0.000
description
4

239000011734
sodium
Substances

0.000
description
4

YCKRFDGAMUMZLT-UHFFFAOYSA-N
Fluorine atom
Chemical compound

[F]
YCKRFDGAMUMZLT-UHFFFAOYSA-N
0.000
description
3

VYPSYNLAJGMNEJ-UHFFFAOYSA-N
Silicium dioxide
Chemical compound

O=[Si]=O
VYPSYNLAJGMNEJ-UHFFFAOYSA-N
0.000
description
3

HEMHJVSKTPXQMS-UHFFFAOYSA-M
Sodium hydroxide
Chemical compound

[OH-].[Na+]
HEMHJVSKTPXQMS-UHFFFAOYSA-M
0.000
description
3

239000011324
bead
Substances

0.000
description
3

230000000052
comparative effect
Effects

0.000
description
3

230000000694
effects
Effects

0.000
description
3

239000012530
fluid
Substances

0.000
description
3

229910052731
fluorine
Inorganic materials

0.000
description
3

239000011737
fluorine
Substances

0.000
description
3

239000000376
reactant
Substances

0.000
description
3

XLYOFNOQVPJJNP-UHFFFAOYSA-N
water
Substances

O
XLYOFNOQVPJJNP-UHFFFAOYSA-N
0.000
description
3

229910016569
AlF 3
Inorganic materials

0.000
description
2

UQSXHKLRYXJYBZ-UHFFFAOYSA-N
Iron oxide
Chemical compound

[Fe]=O
UQSXHKLRYXJYBZ-UHFFFAOYSA-N
0.000
description
2

PXHVJJICTQNCMI-UHFFFAOYSA-N
Nickel
Chemical compound

[Ni]
PXHVJJICTQNCMI-UHFFFAOYSA-N
0.000
description
2

WGLPBDUCMAPZCE-UHFFFAOYSA-N
Trioxochromium
Chemical compound

O=[Cr](=O)=O
WGLPBDUCMAPZCE-UHFFFAOYSA-N
0.000
description
2

239000011651
chromium
Substances

0.000
description
2

229910000423
chromium oxide
Inorganic materials

0.000
description
2

238000007323
disproportionation reaction
Methods

0.000
description
2

WMIYKQLTONQJES-UHFFFAOYSA-N
hexafluoroethane
Chemical compound

FC(F)(F)C(F)(F)F
WMIYKQLTONQJES-UHFFFAOYSA-N
0.000
description
2

239000000843
powder
Substances

0.000
description
2

239000007858
starting material
Substances

0.000
description
2

239000000126
substance
Substances

0.000
description
2

BOSAWIQFTJIYIS-UHFFFAOYSA-N
1,1,1-trichloro-2,2,2-trifluoroethane
Chemical compound

FC(F)(F)C(Cl)(Cl)Cl
BOSAWIQFTJIYIS-UHFFFAOYSA-N
0.000
description
1

YACLCMMBHTUQON-UHFFFAOYSA-N
1-chloro-1-fluoroethane
Chemical class

CC(F)Cl
YACLCMMBHTUQON-UHFFFAOYSA-N
0.000
description
1

101100152636
Caenorhabditis elegans cct-2 gene
Proteins

0.000
description
1

244000025254
Cannabis sativa
Species

0.000
description
1

KZBUYRJDOAKODT-UHFFFAOYSA-N
Chlorine
Chemical compound

ClCl
KZBUYRJDOAKODT-UHFFFAOYSA-N
0.000
description
1

ZAMOUSCENKQFHK-UHFFFAOYSA-N
Chlorine atom
Chemical compound

[Cl]
ZAMOUSCENKQFHK-UHFFFAOYSA-N
0.000
description
1

101100406564
Emericella nidulans (strain FGSC A4 / ATCC 38163 / CBS 112.46 / NRRL 194 / M139) orsC gene
Proteins

0.000
description
1

241000282326
Felis catus
Species

0.000
description
1

102100040837
Galactoside alpha-(1,2)-fucosyltransferase 2
Human genes

0.000
description
1

101000893710
Homo sapiens Galactoside alpha-(1,2)-fucosyltransferase 2
Proteins

0.000
description
1

CYTYCFOTNPOANT-UHFFFAOYSA-N
Perchloroethylene
Chemical group

ClC(Cl)=C(Cl)Cl
CYTYCFOTNPOANT-UHFFFAOYSA-N
0.000
description
1

229910004298
SiO 2
Inorganic materials

0.000
description
1

101000882403
Staphylococcus aureus Enterotoxin type C-2
Proteins

0.000
description
1

150000007513
acids
Chemical class

0.000
description
1

230000017488
activation-induced cell death of T cell
Effects

0.000
description
1

239000004411
aluminium
Substances

0.000
description
1

XAGFODPZIPBFFR-UHFFFAOYSA-N
aluminium
Chemical compound

[Al]
XAGFODPZIPBFFR-UHFFFAOYSA-N
0.000
description
1

229910052782
aluminium
Inorganic materials

0.000
description
1

239000006227
byproduct
Substances

0.000
description
1

229910052801
chlorine
Inorganic materials

0.000
description
1

229910052804
chromium
Inorganic materials

0.000
description
1

150000001875
compounds
Chemical class

0.000
description
1

230000001186
cumulative effect
Effects

0.000
description
1

230000007123
defense
Effects

0.000
description
1

238000005516
engineering process
Methods

0.000
description
1

125000001153
fluoro group
Chemical group

0.000
description
1

UHCBBWUQDAVSMS-UHFFFAOYSA-N
fluoroethane
Chemical compound

CCF
UHCBBWUQDAVSMS-UHFFFAOYSA-N
0.000
description
1

239000008187
granular material
Substances

0.000
description
1

238000010438
heat treatment
Methods

0.000
description
1

229910052742
iron
Inorganic materials

0.000
description
1

229910052759
nickel
Inorganic materials

0.000
description
1

230000000704
physical effect
Effects

0.000
description
1

239000000047
product
Substances

0.000
description
1

239000003380
propellant
Substances

0.000
description
1

239000003507
refrigerant
Substances

0.000
description
1

230000008929
regeneration
Effects

0.000
description
1

238000011069
regeneration method
Methods

0.000
description
1

239000000377
silicon dioxide
Substances

0.000
description
1

239000002904
solvent
Substances

0.000
description
1

Classifications

B—PERFORMING OPERATIONS; TRANSPORTING

B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL

B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds

B01J27/06—Halogens; Compounds thereof

B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium

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

Description

4
A
rr r liil i i I
~I
FORM 10 SPRUSON FERGUSON
I
iP ~i COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE.
65196 Class Int. Class This document contains the amendments made und:r Section 49 and is correct for printing.
Complete Specification Lodged: Accepted: *n *L a S a Published: Priority: Related Art: e
QJ
S
a..
)~7 Name of Applicant: Address of Applicant: Actual Inventor(s): Address for Service:
ATOCHEM
La Defense 10 -4 et 8, Cours Michelet, Puteaux-Hauts-de-Seine, France ROBERT AZERAD, BERNARD CHEMINAL and HENRI MATHAIS Spruson Ferguson, Patent Attorneys, Level 33 St Martins Tower, 31 Market Street, Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: «PROCESS FOR THE SYNTHESIS OF CHLOROPENTAFLUOROETHANE FROM DICHLOROTETRAFLUOROETHANE AND HYDROFLUORIC ACID» The following statement is a full description of this invention, including the best method of performing it known to us I j i h’
ABSTRACT
PROCESS FOR THE SYNTHESIS OF CHLOROPENTAFLUOROETHANE FROM DICHLOROTETRAFLUOROETHANE AND HYDROFLUORIC ACID A gas phase process for the manufacture of chloropentafluoroethane by reacting hydrofluoric acid with dichlorotetrafluoroethane in the presence of a catalyst, the catalyst being prepared by reacting, in a 5 gaseous phase, an alumina in which the sodium oxide content is not more than 300 ppm and the volume of the 0 pores with a radius of at least 40 angstroms is at least 3 0.7 cm /g with hydrofluoric acid or a mixture of hydrofluoric acid and air, nitrogen or a fluoro compound.
so
S
0 0
S
*e 0 the first application………. made in a Convention country in respect of the inenbon tYesuject of the apphcation.
Innt place and date of signtu Declared at Puteaux-Hauts+his THIRD day of NOVEMBER 19 86 de-Seine Signature of deduaant(i) (no aiestiaton required) E E Jean LESOULENGER Notr initl *U Zlr tio Note: Initial all alteratio»n J L A la PROCESS FOR THE SYNTHESIS OF CHLOROPENTAFLUOROETHANE FROM DICHLOROTETRAFLUOROETHANE AND HYDROFLUORIC AICD I The present invention relates to the manufacture of chloropentafluoroethane (C 2
F
5 C1) in the gaseous phase by reacting dichlorotetrafluoroethane (C 2
F
4 Cl 2 with hydrofluoric acid (HF) in the presence of a catalyst.
Chloropentafluoroethane, which is often used as a I solvent, propellant or refrigerant fluid, can be made, for example, from perchloroethylene, chlorine and 0 hydrofluoric acid (East German patent No. 117,580) or by reacting trichlorotrifluoroethane (C 2 F 3 C1 with 10 hydrofluoric acid in the gaseous phase in the presence of aluminium trifluoride (Japanese Publication 48-26,729/73).
S United States Paten. 3,087,974 describes the vapour phase disproportionation of chlorofluoro compounds on a catalyst without the addition of hydrofluoric acid. The o 15 disproportionation of dichlorotetrafluoroethane takes place according to the reaction: 2 C 2 C 1 2
F
4
C
2 CIF5 C 2 C1 3
F
3 The catalyst is activated alumina of high surface area which is treated with a fluorocarbon compound before being used for the disproport.ionation reaction. The conversion of CF 2 C1CF 2 C1 to C 2 C1F 5 does not exceed 34 mole percent and a high proportion of C 2 C1 3
F
3 is produced as a by-product.
2 United States Patent 3,258,500 describes a vapour phase catalysed fluorination using hydrofluoric acid.
According to this patent dichlorotetrafluoroethane
(C
2 Cl1-CF 2 Ci) and hydrofluoric acid in a molar ratio of HF:CF 2 C1-CF 2 C1 of from 4:’1 to 5:1 react at 4000 in one presence of a chromium oxide catalyst. The proportion of hexafluoroethane (C 2
F
6 formed is 0.19 on a molar basis relative to C F C1.
2* A paper by L. Marangoni et al., «Prer ration of 10 chloropentafluoroethane from dichlorotetrafluoroethane» j (Journal of Fluorine Chemistry 19, 1981/82, pages 21 to 34) also describes a chromium oxide-based catalyst for the gas phase manufacture of C 2 F C1 from C 2
F
4 C1 2 and HF.
Ihe degree of conversion of C2C12F 4 is from 72 to 15 molar percent, the yield of C F5[1 is from 89 to 92 molar percent of the products, but the formation of hexafluoroethane is still 8 molar percent based on the amount of C 2
F
5 Cl formed.
A paper by M. Vecchio et al., «Studies on a vapor- 20 phase process for the manufacture of chlorofluoroethanes» (Journal of Fluorine Chemistry, 4, 1974, pages 111 to 139) describes the same reaction as the paper described above but a catalyst based on aluminium fluoride doped with nickel, iron and chromium halides is used. The degree of conversion of C2F4C12 does not exceed 41 molar percent and the molar percentage of C2F5C1 at the reactor outlet is 38 molar percent.
3 -3- SThe catalysts of the prior art are difficult to prepare, and the yields and selectivities of C 2 F5C1 are not good.
The present invention overcomes some or all of these disadvantages and offers a relatively simple, flexible and economical process for producing C 2
F
5 C1.
The present invention provides a process for the manufacture of chloropentafluoroethane which comprises 1 reacting anhydrous hydrofluoric acid with dichlorotetra- *10 fluoroethane in the gaseous phase in the presence of a catalyst wherein the catalyst is prepared by reacting, Sin a gaseous phase, an activated alumina, having a sodium oxide content of not more than 300 ppm and a volume of S*those pores with a radius of at least 40 angstroms of at 3 least 0.7 cm with hydrofluoric acid or a mixture of Shydrofluoric acid and air, nitrogen or a fluoro compound.
*The symmetrical isomer of dichlorotetrafluoroethane
G**
1 is preferred as a starting material.
A high conversion,above 80%,of the starting materials and a high yield of C 2F C- can be obtained.
Another advantage of the process is the catalyst life.
Activated alumina can be produced by controlled heating of alumina hydrate to remove most of the water of formation (Kirk Othmer, Encyclopedia of Chemical Technology, 3rd edition, vol. 2, page 225).
7 -4- The alumina used to prepare the catalyst can be a commercially available alumina. An activated alumina in which the volume of the pores with a radius of at least 40 A is at least 0.7 cm 3 preferably from 0.75 to 1 cm 3 is used. It is advantageous for the alumina to be in the form of granules, beads or extrudates of a size not more than a mm diameter sphere the largest dimension of the alumina is not more than 20 mm), more preferably not more than a few millimetres, for example 0.5 to 3mm to permit convenient handling during the loading and draining of the reactor.
I *The purity of the alumina is generally at least 99.2% Sby weight. The Na20 content of the alumina must be not more than 300 ppm and is preferably as low as possible. It is also advantageous for the alumina to contain not more than 0.5 weight percent silica and not more than 0.2 weight percent iron oxide (Fe 2 0 3 The alumina is converted into a mixture of aluminium trifluoride (AlF 3 and alumina by S. reaction with HF by itself or mixed with air, nitrogen or a fluoro compound.
For example, it is possible to use a mixture of dichlorotetrafluoroethane (C 2 C1 2
F
4 and hydrofluoric acid, which is passed over the alumina at a sufficient temperature to initiate a reaction which converts at least some of the alumina to aluminium trifluoride. It is advantageous to operate at a temperature of from 150 to 500*C.
I;
5 The operation is preferably performed at a pressure uf 0.5 to 2 bars, more preferably at atmospheric pressure, with a contact time of from 5 to 15 seconds. A person skilled in the art can easily carry out the reaction and adjust the proportions of C2F C12 and HF, the temperature, the pressure and the contact time so as to prevent the alumina being damaged by a high temperature produced by the exothermicity of the reaction.
When the gas composition no longer changes after it 10 is passed over the alumina, the alumina has been converted S to the catalyst. It can then be washed with water, if S* appropriate, before being used to effect the fluorination S. of C2F Cl to C2P Cl according to the present invention.
2 4 2 25 According to a preferred embodiment of the invention 15 the catalyst may also be prepared by passing a stream of hot air, nitrogen or a fluoro compound and nydrofluoric acia over S* alumina in a fluidized bed. It is advantagsto crate at a tarpaturC of Sfrom 150 to 500 0 C. A mixture of from 0.1 to 30 molar percent of HF with air, nitrogen or a fluoro compoun, preferably 20 from 1.5 to 3 molar percent, is advantag:eusly employed.
The throughput is advantageously from 200 to 250 moles per hour per litre of catalyst. The operation is most preferably carried out at atmospheric pressure at a temperature of at least 350 0 C. It is convenient to vary the HF concentration in the air, nitrogen or fluoro compound to control the exothermicity of the reaction. When no more HF is consumed, the reaction is stopped and the catalyst is considered to be ready for the fluorination of C 2
F
4 C1 2 6 0.
*Soo b.
0 00 0 *0.
6: 0 0 5i
S
ar Sb.
S
0 _I i 6 The reaction between dichlorotetrafluoroethane
(C
2
F
4 C1 2 and anhydrous hydrofluoric acid (HF) is carried out in the gaseous phase over the catalyst which may be prepared according to either of the above routes. The temperature is advantageously from 350 to 550 0 C and is preferably from 380 to 500 0 C. The molar ratio HF: C 2 C1 2
F
4 is advantageously from 0.5:1 to 1.5:1 anu preferably from 0.9:.1 to 1.1:1. While the operation may be carried out at any pressure, provided that the reactants remain in gaseous 10 phase, it is nevertheless much simpler to operate at a temperature of from 0.5 to 4 bars (0.5×10 to 4×10 Pa) absolute, and preferably at atmospheric pressure or thereabouts, and with a contact time of from 5 to 15 seconds and preferably from 6 to 13 seconds.
The following Examples further illustrate the invention.
In all these Examples,the C 2
F
4 C1 2 employed contains 92.7% of the symmetrical isomer. All percentages are express as molar percentages unless indicated otherwise.
20 Example 1 A pure activated alumina supplied by Kaiser Company (ref. Al 4192) in the form of 0.8 mm extrudates is employed, the characteristics of which are as follows: Volume of pores with a radius of at least 40 A 0.91 cm /g Total BET specific surface 161 m 2 /g Mean pore radius 106 A 7 Apparent density (compacted bulk) 0.47 Surface area of pores with a radius of from 50 to 250 A 105 m2/g Fe203 content 0.08% by weight Si02 content 0.13% by weight content 0.015% by weight 0.12 litres of this alumina are charged as a fixed bed into a tubular reactor having an internal diameter of 28 mm, and it is then converted into catalyst by proceed- S 10 ing as defined in the following table.
r S 0
S
a 6 0*O0 0* B 0 0i:e 0~,i O e 6 r, Reactor Absolute Molar through- Contact Cumulative Temperature pressure put of reactants time time (atmos- in moles/(h x 100 (seconds) (hours) pheres) ml of catalyst) °C !C2C12F4
HF
350 1 0.3 74 0.177 12.8 48 380 1 0.328 0.178 12.7 93 410 1 0.337 0.187 12.2 142 At the end of this treatment, after the oxygen-free acids have been scrubbed with water and an aqueous sodium hydroxide solution, the proportion of C 2
CIF
5 in the gas leaving the reactor reaches 23.6%, whereas it was only 0.7% at 350 0
C.
The reactor temperature is then raised to 450 0
C,
the C2C12F 4 being of the same quality as before.
ees I o. a o* oo 1 ooo o* oooo** oH ooo 8 The results are given in Table I below, where the moi-r throughputs are expressed per 0.1 litre of catalyst, the reactor pressure being 1 bar absolute (1×105 Pa), and the temperature being maintained at 450 0 C. The working time of the catalyst which is shown includes the preliminary step of conversion of alumina into catalyst.
TABLE I OPERATING CONDITIONS I OBTAINEOD Catalyst Mtotar through- Molir Contact Degree of Degree oltr toLar Noltr Specific working put of reac- ratio time conversion of con- ratio ratio ratio output Cm-s tants HF/ (sec- te version CF 6 C2F CL CFbeCr3Cl in grt s cuu- (otes/hour) C onds) 6 2 of of C Cr r o t s l2CL2F6 2CLF5 C2CF CCLFS per hor to iN 100) (A 100) (z 100) per titre SEC2 CLF of cat- X Lyst 165 0.132 0.330 0.40 13.1 90.0 76.9 62.0 0.5 20.1 0.2 316 257 0.268 0.257 1.04 11.6 79.3 85.2 61.4 l’.6 3.9 0.1 310 445 0.254 0.283 0.90 11.3 73.11 5.5 1.7 0.5 4.0 3.1 351 In all the tests described above, the unconverted dichlorotetrafluoroethane (approximately 15% on a molar basis of the C2C12 F 4 compound employed) contains 20 to 10 25% of the symmetrical isomer CF2Cl-CF2Cl.
After 550 hours’ operation under the working conditions described above, and a regeneration with pure air at 450 the catalyst produces results which are absolutely identical to the above.
Example 2 The same activated alumina as in Example 1, in the same physical form of 0.8 mm extrudates, is used and is converted into catalyst by a fluidized bed technique.
4, Do o.
D
ooooo o0@ *o S S~o
SO°°.
S
Soo
S
oooo oooo oooSoS 9 0.125 litre of Kaiser 4192 alumina, i.e. 51.3 g, is heated to 350 0 C in a stream of nitrogen, and the following gas mixture is then introduced for 24 h at atmospheric pressure: air 27.2 moles/h HF 0.77 moles/h.
After 24 hours of this treatment, the catalyst contains 62% of fluorine, that is to say 91.4% of aluminium fluoride and 8.6% of unconverted alumina. Its weight rises to 77.9 grams.
68.1 grams of this catalyst (0.1 litre) are taken to be tested in the same 28-mm diameter tubular reactor as in Example 1, and the procedure of Example 1 is followed.
The results are shown in Table Ii below.
TABLE II OPERATING CONDITIONS RESULTS _OTAINED Catalyst HoLar through- Contact Degree of Degree MoLar Moltr Specific working put of reac- time conversion of con- ratio ratio output Tm tints (sec- version C 2
F
6 4C C 2
F
3
CL
3 in grams (cumu- (motes/hour) onds) HF CCLF of 2 of C 2
CLF
Lative C22 C 2
CL
2 F 4 C2CUS C 2
CLF
5 per hour hours) 2 C 2 to (x 100) (x 100), per Litre C CLF 5 I f cata- 2 Lyst 23.5 0.140 0.377 11.8 89.3 80.4 64.7 1.1 19.2 377 46.5 0.149 0.365 11.8 91.1 80.5 65.1 1.2 18.8 367 66.5 0.140 0.360 12.2 93.4 79.6 63.8 0.7 20. 354 89.5 0.244 0.247 12.4 79.5 87.9 80.8 1.0 5.5 309 111.5 0.223 0.247 12.9 80.2 87.2 79.6 1.0 6.0 304 133.5 0.218 0.247 13.0 53.1 85.8 77.2 1.0 7.5 295 Operating conditions Fixed bed catalyst (volume Temperature: 450 0
C
Pressure: atmospheric 0.1 litre) L 10 The catalyst working time which is shown in this table corresponds to the period beginning with the charging of the reactor with a fixed bed and does not include the conversion of alumina into catalyst.
Example 3 The method of Example 2 is followed, starting with the same activated alumina, except that after the conversion of the alumina into catalyst and charging the reactor with a fixed bed for the fluorination of C2F 4 C1 2 the reaction is started with a molar ratio HF/C 2 Cl 2
F
4 close to 1 instead of 0.4 in Example 2.
I The results are shown in Table III.
I TABLE III OPERATING CONDITIONS RESULTS OBTAINED Catalyst Molar through- Molar Contact Degree of Degree Molar Moar Specific working out of reac- ratio tie conversion of con- ratio rtio output titC tnts Hr/ (sec- I version C F6+ C2 CLt in grams (cumu- (otes/hour) CCl 2F onds) HF CC F of of C CLF l t i ve HF ~C F 2 2 4 C 2CL 2F 4 C t5 2 S pe.rhour hours) 2 to 100) 100) per Litre *C f cat&a o.
a a
I
f a edg 24 0.255 0.243 1.05 13.2 75.4 86.5 79.8 47 0.240 0.245 0.98 12.5 76.8 86.7 79.9 300 302 i Operating conditions Fixed bed catalyst (volume 0.1 litre) prepared as in Example No. 2) Temperature 450 0
C
Pressure: atmospheric The starting method does not alter the catalyst’s activity or selectivity.
F
m~lr~ IIIM l ~a i r 11 The working time shown is the period from the charging of the reactor with a fixed bed and does not include the conversion of alumina into catalyst.
Comparative Example 4 The procedure of Example 2 is followed but using an activated alumina whose pore volume is different from that of the activated alumina used in the process according to the invention; the alumina used is SCM 250, the characteristics of which are: Cnemical purity Na 2 0 800 ppm Fe203 300 ppm SiO 2 200 ppm Physical properties: 15 Form: beads, 2 to 4 mm in diameter Specific surface (BET) :270 m 2 /g Total volume of pores of radius greater than or 3 equal to 40 A 0.63 cm /g 6 Mean pore 20 Bulk density: 0.66 g/ml.
A catalyst is obtained whose A1F 3 content is 87.7% by weight, the remainder being unconverted alumina. The ooo ‘results are shown in Table IV,1; the working times are measured as in Example 2.
TABLE IV,1 0 6
S
OPERATING CONDITIONS RESULTS 0 T-I. N3> TAtI Catalyst MoLar through- motar Contact Degree of Degree Rolar Motar Specific working put of reac- ratio time conversion of con- ratio ratio output time, tants HF/ (see- version C 2
F
6 +CF C 2
F
3
CL
3 in grams (cumu- (motes/hour) C 2
CL
2 F onds) HFj CC .F of of C 2
CLF
tative HF CCt2 C 2 C 2 C 2 5
C
2 CF 5 per hour hours) 2 2 C to 100) (x 100) per titre
C
2
CLF
5 of catat yst 24 0.240 0.243 0.99 12.5 9.0 9.4 6.8 5.8 4.3 48 0.235 0.253 0.93 12.4 10.0 10.3 8.2 2.4 3.6 32 71 0.249 0.253 0.98 12.1 12.7 10.3 7.9 1.9 3.7 31
I
at» least 40 angstroms of at least 0.7 cm with hydirofluoric acid or a mixture of nydrof.iuoric acid and, air,*nitrogerk ,r a fluoro compound.
-12- Operating conditions common to the tests Fixed bed catalyst (volume =0.1 litre) in the form of 2 to 4 mm beads j Temperature =450 0
C
Atmospheric pressure The same SCM 250 alumina is used as spheres of 2 to 4 mm and is converted into catalyst as before, but after the conversion it is reduced mechanically into small pieces of less than 1 mm to approach the size of the Kaiser alumina of Examples 1, 2 and 3. This catalyst is then used as before S. The results are shown in Table IV,2.
TABLE IV,2 0 0 0 0 0 0 0 0 OPERATING CONDITIONS RESULTS OBTAINM Molar through- Molar Contact Degree of Degree Molar Plot ar Specific iiorki’Ag put of reac- ratio time conversion of con- ratio ratio output ti tints HF/ (sec- version C 2 6 +CI4 C F CL 3 in grams (cumu- (motes/hour) C 2
CL
2 F onds) HF C L of of C 2
CIF
tat ive HF CC 2 24 C 2 Ct 2
F
4 C 2 CLF 5 C 2
CIF
5 per hour hours) 224to (x 100) (x 100) per Litre C 2 CLF 5 of cata- Lyst 117 0.232 0.233 1.0 13.0 9.5 10.6 8.4 0.6 2.3 139 0.239 10.234 1.0 12.8 8.9 10.3 8.0 0.6 2.4 29 Temperatures SO0 0 C after the 139th hour 159 0.23g 0.230 1.0 12.1 10.9 120.3 117.2 1.5 1.1 61 operating conditions Fixed bed catalyst (volume 0.1 litre) Temperature 450 0 C up to the 139th hour, then 500 0
C
Atmospheric pressure T 13 The working times shown in the table do not include the time for converting the alumina to catalyst.
Example CS 331-1 alumina sold by Catalysts and Chemicals Europe (CCE) company is employed.
Its chief physical characteristics are as follows: form: extrudates 1/16″ 1.6 mm in diameter 2 active surface area (BET): 255 m /g mean pore diameter: 90 A volume of pores of radius greater than or equal to 40 A:0.76 cm3/g bulk density: 0.60 g/ml.
Na 0 200 ppm S. 2 s Fe 2 0 800 ppm S 2 3 15 Si, 300 ppm The catalyst is prepared as in Example 2, the AlF 3 concentration of the catalyst is 92%, with 8% of unconverted alumina.
The results of the corresponding tests are shown in 20 Table No. V below; tne results obtained are found to be clearly superior to tnose obtained in Comparative Example No. 4 (SCM 250 alumina).
The working times shown do not include the conversion of alumina into catalyst.
TABLE V OPERATING CONDITIONS RESULTS OBTANMJ C CataLyst Motor through- motor contact Degree of *agree Motor Not ar Spec ifi c oki ng put of reac- ratio time conversion of con- ratio ratio output t iL tants Mr/ (sec- 1 version C 2 F 6 C4 Cz2f 3 C3 in grass (cm- (moit/hour) C 2 CLF on1 2F CC F C2tf4 o C 2 CLF5 2 MaFv 2 2t 2. 2 2
C
2 F C 2 CLF C 5 per hour ri 2to (a 100) (m 100) per titre C 2 CIP 5of Catalyst 0.245 0.21.2 1.0 12.5 67.7 76.9 71.5 1.7 5.3 268 48 0.245 0.245 1.0 12.4 66.4 77.0 71.0 1.0 5.4 268 71 0.245 0.245 1.0 12.4 66 .8 76.9 70.7 1.0 5.7 268 0.194 0.243 0.8 1319, .62~ 78.3 70.8 1.2 7.5 266 t
I
i a
C
a a. Cd am ma a a a ate.
o
I
j a @1Cm a: a a em a a a
C
Ca..
C
memo
C
1 operating conditions Fixed zed catalyst (volume 0.1 litre) in the form of 1.6 mm extrudates, prepared as in Example No. 2 Temperature 450 0
C
5 Atmospheric pressure Comparative Example 6 Fluorination of C 2F 4Cl 2with HF according to a process not in accordance with the invention.
instead of taking an alumina and converting it 10 into catalyst as previously, a commercial aluminium trifiuoride powder containing appoximately 8% of alumina is used.
Its chief physicochemical criaracteristics are as follows: 5 mean particle size of the powder: 50 to 80 microns total specific area (BET) 1.6 m 2/g volume of pores of radius greater than or equal to Ai: 0.25 cm. /g.
After this, the procedure is as in the preceding examples of the fluorination of C F C1 with HF, but in 2 4 2 a fluid bed instead of a fixed bed.
The results are collated in Table VI.
TABLE YI OPERATING CONDITIONS RESULTS OBTAINE sO
C
S.
0* aO a *ea 000
*CS
0 0 000 0
*S
Catalyst Noltar through- Notar Conitact Degree of Pegree oaI ar otar Specific ;uorking put of reac- ratio time conversion of con- ratio ratio output tiML_ tanti 1F/ (sec- version C2 6 2 CL in gross cuu- (moLes hour) CCL F onds) CoF off C2 r CL2 2 iv L C CLF C t htrve u 2 2 4 C 2
CL
2
P
4 2 5 2 ClFS per hour orsC 4 to (1 100) (a 100) per titre
C
2 CLf of catE- I 121 y 24 0.357 0.358 1.0 11.8 7.0 0.2 0.1 0 0 0.4 4 0.351 0.378 0.9 11.6 2.0 0.1 0.1 0 0 0.4 70 0.351 0.376 0.9 11.6 4.1 0.1 0.1 0 0 0.4 92 0.360 0.368 1.0 10.8 5.4 0.2 1 0.1 0 I 0 0.4 5 Operating conditions Catalysts in tne form of a fluid bed (volume 0U.14 litre) with a mean particle size of 50 to 80 microns Temperature 450 0
C
Atmospheric pressure 10 Example 7 Tne procedure of Example 2 is followed, using the same type of alumina (Kaiser 4192), but working with a shorter contact time.
The results are shown in Table VII, where the workling times do not include the time for converting the alumina into catalyst.
It is found that the specific output of C 2 C1F can be considerably increased without harming the yield.
16 TABLE VII
I
I
mm .aa.
S.
ar a.
a a. 0 a.
a S a a ai Saas OPEATING CONDITIONS RESULTS OBTAINE iat yst Ito r through- iotar Contact Degree of egre. Rotar rotaor Specific rking put of reac- ratio time conversion of con- ratio ratio output imnC cant MF/ (sec- z version C I 6 CF CL 3 in grams cuu- (oote/Ihour) C 2
CL
2
F
4 ands) Fof of C L ra) F C2CL 2F C2 2 C C2 4 C 2 CLI C 2 CF per hour to (N 100) ii 100) per Litre C CL of catasLyst 24 0.349 0.375 0.93 8.4 60.3 65.4 60.2 1.0 7.5 0.367 0.373 0.98 8.2 $9.5 67.2 62.1 0.5 60.2 72..5 0.521 0.501 1.04 5.9 SI.? 60.9 57.1 .i 42.0 5 0.500 0.495 1.01 6.4 54.4 62.7 58.5 1 0.7 6.7 447.4 Operating conditions Fixed bed catalysts (volume 0.1 litre) in the form of 0.8 mm ext-rudates Temperature 450 0
C
5 Atmospheric pressure The following Table ViII collates results obtained under analogous operating conditions and shows the effect of the Na 2 0 content.
The volume of the pores with a radius of at least 40R in the catalysts is the same as in Example 1, i.e. 0.91 3c cm /g.
4 1~ S. 0
S..
0
S
0* 0
S
S..
S
*5 *SS S S S* S *S S S S S 5 S 5 5 S S 5 5* S S TABLE VIII OPERATING CONDITIONS RESULTS OBTAINED Molar throughput Molar Contact Degree of Degree of Molar Specific output Na 0 of reactants ratio time conversion conversion ratio in grams of C 2
CIF
conient (moles/hour) HF/C 2 Cl 2
F
4 (seconds) of C 2 C1F. C 2 C1 3
F
3 per hour per 2 2% to2CCl2F to C Cl3F litre of (ppm) HF C 2 C1 2
F
4 HF C 2 C1 2 4 (x 2 0 catalyst 150 0.449 0.429 1.05 7.4 52.1 61.1 57.9 5.5 383.8 930 0.411 0.428 0.96 7.2 7.8 8.1 7.7 5.2 50.9 Operating conditions Fixed bed catalysts (volume 0.1 litre) in the form of 0.8 mm extrudates Temperature 450°C Atmospheric pressure 11e unt

Claims (15)

1. A process for tne manufacture of chloropenta- fluoroethane which comprises reacting anhydrous hydrofluoric acid with dichlorotetrafluoroethane in the gaseous phase in the presence of a catalyst, wherein the catalyst is preparea by reacting, in a gaseous phase, an activated alumina, having a sodium oxide content of not more than 300 ppm and a volume of those pures with a radius of *3 at least 40 angstroms of at least 0.7 cm with S hydrofluoric acid or a mixture of nydrofluoric acid and 10 air, nitrogen or a fluoro compound.

2. A process according to claim 1, wherein the alumina has a volume of tnose pores witn a radius of at *3 least 40 A of from 0.75 to 1 cm /g.

3. A process according to claim 1 or 2, wherein the purity ot the alumina is at least 99.2% by weight.

4. A process according to any one of claims 1 to 3, o.oo wherein tne alumina is in the form of particles of a size smaller tnan a 20 mm diameter sphere. A process according to any one of claims 1 to 4, wherein tne catalyst is prepared Dy reacting a mixture of air or nitrogen and hydrofluoric acid with alumina at a temperature of from 150 to 500 0 C.

6. A process according to claim 5, wherein the HF content in the mixture of HF and air or nitrogen is from 0.1 to 30 molar percent.

7. A process according to claim 6, wherein the HF content is from 1.5 to 3 molar percent.

8. A process according to any one of claims 5 to 7, wherein the reaction is carried out at atmospheric pressure and a temperature of at least 350°C.

9. A process according to any one of claims 1 to 4, wherein the catalyst is prepared by reacting a mixture of hydrofluoric acid and dichlorotetrafluoroethane in the gaseous phase with alumina at a temperature of from 150 to 10 500°C. S 10. A process according to claim 9, wherein the reaction is carried out at atmospheric pressure with a S* contact time of from 5 to 15 seconds.

11. A process according to any one of claims 1 to 10, wherein the fluorination of dichlorotetrafluoroethane with HF is carried out with a molar ratio HF: dichlorotetrafluoroethane of from 0.5:1 to 1.5:1 at a S*I* temperature of from 350 to 550°C.

12. A process according to claim 11, wherein the molar ratio is from 0.9:1 to 1.1:1.

13. A process according to claim 11 or 12, wherein o 0 the temperature is from 380° to 500°.

14. A process according to any one of claims 11 to 13, wherein the reaction is carried out at a temperature of from 0.5 to 4 bars (0.5×10 5 to 4×10 5 Pa) absolute. i Sr’ 20 A process according to claim 14, wherein the reaction is carried out at atmospheric prc sure with a contact time of from 5 to 15 seconds.

16. A process according to claim 15, wherein the contact time is from 6 to 13 seconds.

17. A process according to claim 1 substantially as hereinbefore described in any one of Examples 1 to 3,5 7.

18. Chloropentafluoroethane whenever prepared according to a process as claimed in any one of the 10 preceding claims. DATED this ELEVENTH day of NOVEMBER 1986 ATOCHEM Patent Attorneys for the Applicant SPRUSON FERGUSON eg B 0 0 O*00 J pi

AU65186/86A
1985-11-15
1986-11-14
Process for the synthesis of chloropentafluoroethane from dichlorotetrafluoroethane and hydrofluoric acid

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PROCESS FOR THE SYNTHESIS OF CHLOROPENTAFLUOROETHANE FROM DICHLOROTETRAFLUOROETHANE AND FLUORHYDRIC ACID

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1985-11-15

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GAS-MAKING PROCESS OF CHLOROPENTAFLURETAN

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1988-05-30
1991-02-26
Central Glass Company, Limited
Method of preparing 1,1,1,2-tetrafluoroethane from 1,1-dichloro-1,2,2,2-tetrafluoroethane

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A catalyst for halogen exchange in halohydrocarbons and for acid/base reactions

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1993-11-01
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E. I. Du Pont De Nemours And Company
Azeotropes of chlorofluoroethanes of the formula CF3 CC12+x ub. F.s1-x with HF and manufacturing processes therewith

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1995-06-29
1997-08-01
Atochem Elf Sa

PROCESS FOR PRODUCING DIFLUOROMETHANE

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1997-05-22
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Hoechst Ag
Process for preparing aliphatic fluorine compounds

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Process for fluorinating halohydro-carbons

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Process for the production of chloropentafluoroethane

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CONTINUOUS PROCESS FOR GAS PHASE PREPARATION OF TRICHLOROTRIFLUORETHANE, DICHLOROTETRAFLUORETHANE AND MONOCHLOROPENTAFLUORETHANE IN CONTROLLED PROPORTIONS

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