DE1618290C - Process for the production of 1-chloro-1-fluoroethane - Google Patents

Description

1 618 294
3 4

the otherwise required effort to reduce the ice 1 1 regenerated contact with hydrogen and a ^p . Separate separation of the water formed during the reduction, consisting of about 95 percent by weight of η-hexane. In the following examples, the invention is explained in more detail using a catalyst of the following composition. acts:

Weight percent

Cr ₂ O ₅ 10

Al ₂ O ₃ 84

SiO ₂ 2

K ₂ O 4

Table 1

Reaction temperature ^{, 0 C}

Space velocity (V / V / hour)

Liquid product based on input

(Weight percent)

Benzene in the liquid product (percent by weight) .. Benzene, based on the input (percent by weight) Gas, based on the input (percent by weight) .. Hydrogen content in the cracked gas (percent by volume) Carbon based on usage and per hour

(Weight percent)

Trial number 2 3 4th 1 570 547 570 530 0.6 0.8 0.8 0.6 83.0 87.4 83.1 89.9 90.5 69.0 80.0 68.0 75.2 61.5 66.5 61.0 15.2 11.3 15.4 9.0 94.6 95.0 93.6 96.0 1.8 1.3 · 1.5 1.1

560
1.05

88.0
65.7
57.8
10.8
95.9

1.2

This table also makes it clear that the 30 One finds that in agreement with the drive the invention from a practically complete literature the cyclo-aromatization present in petroleum products (Experiment 2) up to a high pentane, predominantly alkyl-substituted cyclopentane, Aromatic enrichment can be varied. have a disruptive effect in high concentrations.

Example 2

A technical gasoline fraction with the composition

Weight percent

n-pentane 9

i-pentane 1.1

η-hexane 55.0

2-methylpentane 9.0

3-methylpentane 7.0

Methylcyclopentane 4.5

Cyclohexane 5.5

Benzene 3.0

n-heptane 2,3

other KWW 3.6

is reacted with the catalyst specified in Example 1 in a fixed bed reactor.

Reaction ^{temperature (0} C) 550

Space velocity (v / v / hour) 0.6

Liquid product, based on use

(Weight percent) 84.3

Benzene in the liquid product

(Weight percent) 52.3

Benzene based on insert

(Weight percent) 43.1

Toluene, based on insert

(Weight percent) 3.2

Gas, based on use

(Weight percent) 10.5

Hydrogen content in the cracked gas

(Percent by volume) 95.0

Carbon based on input (weight percent) 5.2

Example 3

The starting product according to Example 1 is in a fluidized bed apparatus of the reaction on a Catalyst of the composition mentioned in Example 1 subjected. The reaction conditions and The results are shown in Table 2.

Table 2 Trial number 2 1 561 45 548 0.84 Reaction ^{temperature (0} C) 0.65 Space velocity (V / V / hour) 87.1 Liquid product, based on Ein 87.0 50 rate (weight percent) 82.5 Benzene in the liquid product 84.7 (Weight percent) 71.6 Benzene based on insert 73.7 (Weight percent) 11.7 55 Gas, based on use 12.0 (Weight percent) 97.0 Hydrogen content in the cracked gas 97.0 (Volume percentage) Carbon in percent by weight, 1.2 60 based on use and per 0.9 lesson

Example 4

Analogously to Example 1, the reaction at 550 to 551 ° C with a space velocity of 0.63 to 0.64 (v / v / hour) performed. After 2 catalyst cycles (reaction and regeneration) there is a benzene yield of 70.0 percent by weight, based on the

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Use, received. After 80 cycles, the benzene yield drops to 57 percent by weight. 192 g of the tired catalyst (bulk volume about 200 cm ^s , grain size 5 mm) are then _{soaked in a solution of 5.76 g of K 8} Cr ₈ O in 100 ml of water, dried for 2 hours at 120 ° C. and then for 4 hours Annealed at 450 ° C. With the catalyst reactivated in this way, the process is carried out as above. After 2 cycles, a benzene yield of 69.2 percent by weight is obtained.

Claims (5)

1 2 Thus it is very difficult to increase the conversion of claims: vinyl chloride to over 90%. Another disadvantage is that the 1. Process for the production of 1-chloro-1- lysator substance used in anhydrous fluorohydrofluoroethane by reacting vinyl chloride with 5 substance also acts as a fluorine-replacing agent. If hydrogen fluoride in the presence of fluorosulfone, for example vinyl chloride with hydrogen fluoride under acid as a catalyst, characterized by using fluorosulfonic acid as a catalyst, that vinyl chloride is reacted with water, 1,1-difluoroethane is formed in the free hydrogen fluoride in the vapor phase Gas product to the extent of 5 to 25%. This is also the case at a temperature of 20 to 100 ^° C. in the presence if sulfuric acid is used as the catalyst of a solid catalyst, consisting of one, since fluorosulfonic acid is formed according to -5 to 60 percent by weight (based on the final reaction equation will:
Catalyst) fluorosulfonic acid impregnated Ak- ", -. . " _Cn . _un , _{υ <: η P}
tivkohle, converts. 124 2 3 2. The method according to claim 1, characterized in that the object of the invention is to create a draws that one hydrogen fluoride and vinyl process for the preparation of 1-chloro-1-fluoroethane chloride in a molar ratio of 1: 1 to 10: 1, in high yields by conversion of vinyl preferably 3: 1 to 7: 1. chloride with hydrogen fluoride avoiding 3. The method according to any one of claims 1 and 2, standing disadvantages. characterized in that the reaction 20 It is known that the catalyst, which by with a contact time of 1 to 120 seconds, impregnation of a carrier, for example of SiIi- preferably 5 to 20 seconds. cium dioxide, or diatomaceous earth, with sulfuric acid 4. The method according to any one of claims 1 to 3, or phosphoric acid was prepared, and that a characterized in that the reaction is carried out containing supports containing sublimed aluminum chloride in the presence of a solid catalyst, 25 as a Brönsted acid or Lewis acid in one of these by immersing activated carbon in fluorous reaction the polymerization of the unsaturated sulfonic acid and subsequent drying cause starting materials or their alkylation and has been presented. that therefore such a catalyst in these cases 5. The method according to any one of claims 1 to 3, is very effective. characterized in that the implementation 30 There was nothing about the expected Erin Presence of a catalyst that is known by results when such a solid acid kata immersion of activated carbon in a liquid water analyzer in the production of 1-chloro-l-fluoroethane free hydrogen fluoride with a corresponding one by reacting vinyl chloride with water fluoride content of fluorosulfonic acid. fabric is used. Accordingly, so far, how 35 described above, the preparation of 1-chloro-1-fluoroethane by blowing in vinyl chloride or consisting of a gas mixture of vinyl chloride with hydrogen fluoride in a liquid catalyst from liquid hydrogen fluoride and fluorosulfonic acid It is known that 1-chloro-l-fluoroethane can be carried out with 40 or sulfuric acid. Reaction of vinyl chloride with hydrogen fluoride in According to the invention, a process for the preparation Absence of a catalyst under pressure can produce position of 1-chloro-l-fluoroethane by reaction (see. German Patent 859 887). This procedure, known from vinyl chloride with hydrogen fluoride in the presence, is, however, created in technical terms and from fluorosulfonic acid as a catalyst, which is inferior in economic terms, since the extent is characterized by the fact that vinyl chloride of the reaction and the yield of 1-chloro-l-fluoro with anhydrous hydrogen fluoride in the steam ethane are unsatisfactory. phase at a temperature of 20 to 100 ⁰ C, preferably On the other hand, it is known to ^{react from 20 to 70 0} C, in the presence of a solid Kata-vinyl chloride and hydrogen fluoride in an anhydrous lysators, consisting of a 5 to 60 weight hydrogen fluoride using a 50 percent acid, preferably 10 to 45 Percent by weight of active substance, for example of fluorosulfonic acid, (based on the finished catalyst) to run fluorosulfon as a catalyst (cf. USA patent specification acid-impregnated activated carbon, converts.
2,462,359). According to this procedure, a gas is found that by fixing the Mixture of vinyl chloride and hydrogen fluoride in acid catalyst on activated carbon occurs a liquid catalyst blown in, or vinyl 55 from side reactions caused by the very high level of quenching chloride gas is in liquid anhydrous fluorinity of 1-chloro-l-fluoroethane in the liquid hydrogen containing the catalyst dissolved in a catalyst is restricted. the blown. However, since 1-chloro-1-fluoroethane in fluorine production of the by-product 1,1-difluoroethane is hydrogen and the catalyst is easily dissolved, suppressed, and at the same time the contact may occur an undesirable side reaction, whereby the duration of the reaction system is better regulated, the liquid catalyst brown at the beginning of the reaction. becomes discolored. In addition, the viscosity of the reacting catalyst can be achieved by impregnating a tion fluid gradually increased. Therefore, some activated carbon must be made with fluorosulfonic acid, of the catalyst in such a reaction die used according to the invention system every 50 to 100 hours through fresh catalyst 65 activated carbon can use any of the technical preservers be replaced. Since, in addition, the reaction will be borrowed coal products. The reaction will go through system is a vapor-liquid contact system that does not affect the shape and size of the coal particles the regulation of the contact time difficult. flows. However, since the implementation is usually in one