DE1219473B - Process for the production of unsaturated chlorinated hydrocarbons with 2 to 4 carbon atoms - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

PATENT OFFICE

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Ιψ. CL:

C07c

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: PeutscheKl ,; 12 «-

1219473
P29425IVb / 12o
May 16, 1962
June 23, 1966

Deaeon processes or oxychlorination processes are understood to be processes catalyzed by metal halides in which gaseous hydrogen chloride or; Chlorine as a chlorinating agent. Finds one: the process under consideration consists in. The. Chlorination of a hydrocarbon or chlorinated hydrocarbon with hydrogen chloride and ' an oxygen-containing' gas such as' liTlft or elemental oxygen. The conversion takes place in the presence of a metal halide catalyst, such as copper chloride, which is distributed on a suitable carrier material. The essentials of this _; Oxychlorination is that ^{r is} the hydrogen chloride. ? u ChloE-uiid - water that is oxidized> and: the chlorine expands to form chlorinated hydrocarbons and HCt with the organic carbon hydrogen; or the. Chlorinated organic substances SAmsetzii 'According to another form of the Oxychlotriejungsveriahrens mxd- j elementary chlorine, as .. Begghiekungsmaterial used In this process, hydrogen chloride is used by chlorination of the hydrocarbon. and / or, ßhloxkohlenwasserstoffs -.- ierzeugte, which brought together with the elemental chlorine of the iatalytisehen reaction

t:; Mian has found that -in an oxychlorination process using certain hydrocarbons ^! and / or chlorinated hydrocarbons. as a charge of general mixtures of chlorinated carbon-water§t0ffd.eriyate. of the supplied hydrocarbon: and / or: chlorinated hydrocarbons are formed. The exact composition can vary widely, and it is extremely difficult in such a process to produce chlorinated hydrocarbon derivatives which mainly consist of one or more of the desired products. This is particularly the case when fully saturated carbon pulp and mostly more unsaturated molybdenum hydrocarbons. are to be produced «.; . ■.; - Now .5 it was .. © ia;: iProcedure for? Production of unsaturated! Chlorinated hydrocarbons r with ·> -2 to · ^ • J carbon atoms. -Jurch: Oxychlorination. Of the * corresponding saturated hydrocarbons = with chlorine or chlorine, and one containing oxygen; presence of. Metal halides as a catalyst? gefiinde that is "characterized igekenazeiehnet · that dieQxychlorierung beis470 C -and a ratio desrKetaiysatofgewiphts (in - grams) ⁰ to 550 performs -to feed rate of the total gases (in 1 per minute) of 30 to 420; · ■ · ;; ■ - · ---.

For the oxychlorination solutions: all known oxychlorination catalysts or Kata processes for the production of unsaturated
Chlorinated hydrocarbons with 2 to 4 "carbon atoms

Applicant:

Pittsburgh Plate Glass Company,.

Pittsburgh, Pa. (V.StA.).

Representative: .:.....,

Dr. W. Beil, A. Hoeppener and Dr. H. J. Wolff, lawyers,

Frankfurt / M.-Höchst, Adelonstr. 58 "',

Named as inventor:
Robert E. McGreevy,
Joseph E. Milam,
NewMaritinsville, W. Va. (V. St. A.)

Claimed priority:

V, St! Ν. America May 16, 1961 (110 348) -

Deacon lysers, which are distributed on a suitable carrier, are used. Normally, fine · oxychlorination catalysts used are metal halides, preferably chlorides of a polyvalent metal such as'^.'Kupfer; - iron and chrome. These metal halides, preferably in the form of - of. Chlorides can be used alone or in a mixture with others: metal halides, -ζ. R alkali chlorides or alkaline earth chlorides or mixtures thereof can be used. A particularly effective catalyst: for. ^; the reactions to be considered here • is a catalyst: made of copper chloride and potassium chloride, distributed on a porous support. The catalysts used in the process according to the invention generally contain: Copper in a larger amount, ie 4 to 12 percent by weight of copper, based on the impregnated particle. ■:. ■::. ·· · ': Als'Trägersubstanz for:.. .the to carry out the inventive oxychlorination used Kätalysatoren ^ for example, silica - Toneide, fuller's earth, diatomaceous earth, pumice stone and other materials of this ^one AICB use What is -gewählt the individual carriers depends-'Zum < ^r largely depends on the desired conversion, i.e. on whether a solid layer or a fluidized bed is used and, if fluidized beds are used, on the speed of the gases, the strength of the

609 580/431

3 4

Vehicle and similar factors. For fluidized bed hydrogens. Processes HCl as a chlorinating agent if a specially treated fuller's earth has turned, the charge ratio is that in proved to be a particularly effective carrier. For solid - the zone of catalytic oxychlorination layer process has become a calcined diatome- brought gaseous substances in general between earth has proven to be an extremely effective carrier. 5 0.6 moles of HCl per mole of hydrocarbon and / or The calcined diatomaceous earth is similar to chlorinated hydrocarbons and 4.0 moles of HCl per mole Fluidized bed process proven as an effective carrier. Hydrocarbon. Preferably the molar

The used catalytic ratio of chlorine to hydrocarbon is regulated in such a way that Material is according to known methods in here that 0.5 moles of chlorine to 1 mole of hydrocarbon unclaimed manner on the carrier come, whereby ethylenically unsaturated coals bring. Low chlorine hydrogens such as vinyl

The oxychlorination chloride and allyl chloride which come into consideration here are formed; If the method of the invention is used in the form of solid-layer reactions, the catalyst according to the invention can be carried out; in performing mainly these products are produced. If HCl is used as solid-layer conversions in accordance with the chlorinating agent present, the reaction ratio of HCl to hydrocarbon and / or vessels are normally used which are quite long compared to their internal chlorinated hydrocarbon by monitoring the diameter. The length of this feed ratio is regulated so that there is generally 1.0 mol of HCl for 1 mol of reaction vessels. It is obvious to those skilled in the art for up to six hundred times their inner diameter, 20 that the Molveres can use tubes with an inner diameter ratio of chlorinating agent to hydrocarbon of 6 to 205 mm. It is preferably regulated accordingly so that the reaction vessels described above with an internal ratio for HCl and Cl _{2 are obtained} if a knife of 25 to 76 mm is used for _{solid-layer processes using mixtures of HCl and Cl 2} ; used thereby. The reaction vessels are usually 25 it must be taken into account in what amount of each ChIo from mild steel, nickel or other suitable lubricant is contained in the mixture supplied. Material is made that has a certain corrosion resistance, as far as oxygen is brought into the oxychlorination zones with respect to those used, the feed ratio of gases is; However, metal vessels can also oxygen to chlorine by monitoring the presence, which regulates a suitable corrosion rate of these substances on the inside, solid coating, for example made of ceramic, that the reaction zones have 0.2 to 2.4 mol of oxygen substance, or also glass vessels. per mole of chlorine are supplied. The relationship

To convert unsaturated chlorinated hydrocarbons from oxygen to chlorine remains a matter of course

hold, the temperature in the reaction zone must be the same if air is used, but the

be carefully and carefully controlled. The preferred amount of oxygen-containing gas is that amount

wise is increased at temperatures between 485 and 510 ⁰ C, in which other gases are present in the air

worked because you get the best results, are. If air is used as the feed gas and chlorine is used as the

if a temperature of 500 or around 500 ⁰ C chlorinating agent is used, then in general

adheres to. If you work at temperatures below a volume ratio of air to chlorine in the range

of the specified range, regardless of this, in 40 from 1 to 12 volumes per volume of chlorine selected,

as far as the reaction is otherwise regulated, so preferably oxygen is used in such amounts

one obtains predominantly saturated hydrocarbons that are supplied with 1 mole of oxygen for 1 mole of chlorine

fabrics. On the other hand, if the temperatures are above it. With air, each volume of chlorine becomes 5 volumes

the specified upper limit, so burn large air supplied. If HCl is used instead of chlorine

Amounts of added hydrocarbons are used in the feed, the ratio of

Reaction zone. Oxygen to HCl to 0.2 to 2.4 moles of oxygen each

Set in moles of HCl feed to regulate temperatures. Preferably will

Considered reaction zones, this ratio can be chosen so that 1 mole of O ₂ to 1 mole

use any known method. HCl is coming. If air is used, the

The chlorine introduced into the reaction zone 50 feed rates regulated so that 1 to

medium is 70 to 90% of the feed - 12 volumes of air to 1 volume of HCl and preferably

amount used. Using the chlorination method, get 5 volumes of air to 1 volume of HCl,

means is that amount that the reaction zone draws- Likewise, the ratio w: f must be within

led chlorinating agent meant, which are kept as certain limits to a

Chlorinated hydrocarbon product is obtained. It turns out that 55 correct use of the inventively used

ensure that the chlorinated hydrocarbons obtained in the chlorinating agent. The for the rea-

Gases required mainly from unsaturated chlorinated hydrocarbons are produced in such quantities

substance exist when the use between 70 and introduced into the oxychlorination zones that are

90 ° / _{0 of} the amount introduced into the reaction zone gives a ratio w : / between 30 and 120. Of the

lies. Preferably, the use of the chlorine expression ratio w: f is that

tion agent during the oxy weight described herein used in the catalyst layer

Chlorination reactions at 73 to 85 ° / ₀ . Catalyst divided by the flow rate

If chlorine is used as the chlorinating agent, then the total amount supplied to the catalyst layer

the feed ratio of the gases in the zone is according to the following formula:

catalytic oxychlorination introduced gas 65

shaped substances generally between 0.3 molar weight of the catalyst (grams) [w] _{= χ}

Chlorine per mole of hydrocarbon and / or chlorine feed rate of the total gases

hydrocarbon and 2.0 moles of chlorine per mole of carbon (l / min) [/]

A ratio w : / of 55.5 is preferably chosen.

The organic compounds prepared according to the reactions described here can be used in can be obtained in a known manner.

example 1
A. Preparation of the catalyst

Calcined diatomaceous earth with a particle size between 0.175 and 0.417 mm was used as the carrier substance for the catalyst. 400 g of this carrier was placed in a rotary drum, the plant was set in motion and heated to a temperature of 14O ⁰ C. A stock solution was prepared by dissolving 440 g of CuCl ₂ · 2 H ₂ O, 186 g of KCl in 1000 cm ^{3 of} water. 294 g of the stock solution containing copper chloride and potassium chloride was diluted to 1,333 cm ³ with distilled water. The diluted solution was added dropwise to the vehicle in the rotating drum while the rotating drum was continuously heated. After addition of the solution the impregnated carrier in the rotary drum was dried by this was rotated for another 30 minutes while heating the contents to a temperature of 140 ⁰ C. Based on the total weight of the support, the finished catalyst contained 6 percent by weight copper on an anhydrous basis.

B. Oxychlorination

A tube with an inner diameter of 50.8 mm and a height of 152.4 cm was used as the Fluidized bed reactor used. The reactor was started from a point 30 cm from the bottom of the vessel was removed, filled with the catalyst prepared according to A at a height of 45 cm. The whole The reactor tube was placed vertically in an electric furnace with the lower and upper ends of the Reaction vessel protruded from the top or bottom of the furnace, so that the entire, in the reactor located catalyst layer within the elec-

ia Irish stove. At the bottom of the reactor below a perforated plate serving as a distribution plate, 30 cm above the bottom of the reactor Glass pane was an inlet opening. The opening was through an ordinary gas pipe three lines, one each for ethane, one for chlorine or HCl and one for air. The dem Gases fed into the reactor through the opening flowed through the distributor plate into the bed into it. A line to pull off the resulting

ao products were in the upper part of the reaction vessel, and all gaseous products were through removed this line from the reaction vessel. The withdrawn, gaseous products were through two coolers mounted one behind the other and in one

a5 normal collecting vessel, in which HCl and water were collected. The gases were then passed through several traps cooled with a mixture of dry ice and acetone, in which the chlorinated hydrocarbons were collected in isooctane as a solvent. A number of experiments were carried out; in all experiments the temperature was 498 to 501 ^° C., the ratio w: f was 55.5. The results of these tests are summarized in Table I:

Table 1

Average temperature, ⁰ C

Gas feed ratio (molar):

C ₂ H ₆

HCl

O ₂

Product chromatographic analysis, mole percent

Overall, grams

C ₂ H ₄ Cl ₂

C ₂ H ₃ Cl ₃

C ₂ H ₂ Cl ₄

C ₂ JdL ₃ C /!

¹ C ₂ H ₂ Cl ₂

C ₂ HCl ₃

C ₂ Cl ₄

CHCl ₃

CCl ₄

CH ₃ Cl

C ₂ H ₅ Cl

HCl used, in%

Example 2

Using the catalyst from Example 1, A and using the apparatus of Example 1, B was a series of experiments with ethane, chlorine

2 Attempt no. 4th 5 1 501 3 500 498 500 1.0 501 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 784 1.0 704 729 707 10.5 730 16.2 11.0 13.2 15.0 0.2 1.6 3.4 0.2 0.1 0.1 0.0 44.8 0.1 45.9 49.2 50.3 3.2 48.4 3.4 2.8 1.8 1.8 3.2 1.7 1.4 0.1 0.7 1.8 0.8 1.0 0.2 4.7 1.0 4.1 3.1 3.3 2.8 3.5 3.2 1.8 2.8 4.2 2.5 2.6 2.9 2.8 24.1 3.2 21.7 25.2 22.0 87.4 21.2 78.2 77.7 73.1 80.1

500

762

45.7
7.0
1.5
0.6
4.3
2.6
2.0

and air fed at a ratio w '· f of 55. An average temperature of 500 ^° C. was maintained during the reaction. The results are summarized in the following table II:

I'219 473

Tabelie'li

Catalyst, - wvf-Λ, ': ...,. ;;.;.: ......: ;;'rs;55.5;:

• Average temperature: ° C .. y. ; v -500 -

• Gas feed ratio

C ₂ Mr.

1.00
.0.50.
5.00

■ Content of ·· unsaturated ■■■ chlorinated ■ '''-' ■
Hydrocarbons .with .: 2 carbon - .. · f.- ■:

: substance breathing. 65

Average. · Number "· vx> n chlorine--. ■: v /.
atoms in unsaturated chlorinated; :.
Hydrocarbons with; 2 carbon ··: "·: ::.
atoms - "'·.-....-.:. ■■>. ■ .. iV .'...: .. ί.; ..; ..... 1,3-content, of saturated chlorinated
Hydrocarbons with 2 carbon - :: - "::
■ atoms - ».-. ^ · ,, .... ■? .. :: Λ.:. '~. ::.;.;. " ..: ■: ... 28:
, Average number: of: Chlorine:.:. ·.
atoms in the saturated chlorinated ones

Hydrocarbons with 2 carbon

atoms.; ; ---- 4; 5-

Cl ₂ , used 76

Vinyl chloride made up 73 percent by weight of the unsaturated chlorinated: hydrocarbons with 2 carbon atoms.

If butane is fed in instead of ethane in Examples 1 and 2, the predominant amount is also obtained Amount of unsaturated chlorinated hydrocarbons, while only small amounts of saturated chlorinated hydrocarbons be generated.

Example 3

A stainless steel tube with a diameter of 2.5 cm was filled with the catalyst prepared according to Example 1, A at a height of 5 cm. The reaction tube was charged with propane, chlorine and air in molar ratios of 1.025 and 2.18, respectively. The reaction gases remained in the reaction zone at a temperature of 504 ° C. for 1 second. The yield of chlorinated product was 30%, based on the propane used, and the utilization of the chlorine was 79.4%, based on the chlorine fed in.

Example4

441 g CuCl ₂ -2 H ₂ O, 186.8 g KCl were dissolved in 1000 cm ^{3 of} distilled water. 1000 cm ^{3 of} calcined diatomaceous earth in the form of certain cylindrical particles were added to this solution. The particles were 6.35 mm long and 6.35 mm in diameter. After the particles were soaked with the solution for 24 hours, the remaining liquid was drained and the particles were allowed to air dry.

A tube made of stainless steel with an inner diameter of 25 mm and a length of 152 cm was filled with the catalyst at a layer height of 66 cm. The reactor was placed vertically and surrounded by a steel jacket. The jacket was coated with a mixture of salts (sodium nitrate, sodium nitrite and sodium chloride); and these salts were kept in a molten state during the operation. Heating tapes were put around the cloak, around it; heating during commissioning, and a heat regulator

was connected to the radiators and to the molten salt to ensure that the salt was kept at a temperature of 450 ° C during the operation. '■ ■ - ■ ■; · :: -. :: · -:' - ^:; The starting products were introduced into the tube through an inlet opening at the lower end of the tube, and the end products were drawn off at the upper end through a discharge line. The amount of gas fed in was measured with a HiKe by rotameter ίο, and the withdrawn 'products were cleaned with water and lye' *, and then condensed in 'cooled' traps with dry ice - acetone.

Using this device and this catalyst: "Several tests were carried out with ethane, chlorine and air, producing vinyl chloride. The results are compiled in" the following Table III: ^% "

Table ΠΪ

Loading speed
(Moles per minute)

Ethane

chlorine

Air .,.

Temperature (average),
Contact time *, seconds ...

Productivity (basis: mole percent
supplied Äthans)

Vinyl chloride

Ethyl chloride

Perchlorethylene ...
Trichlorethylene ...
1,2-dichloroethane ..

Dichloroethylene

1,1,2-trichloroethane

chloroform

Methylene chloride ...

Methyl chloride

Ethylene _>;

Burned ethane

Attempt no.
1 I 2

0.024

0.104

485
1.2

32.8
4.43
0.13
0.38
2.87
2.35
0.26
0.04
1.15
2.62
44.3
16.2

0.020 0.009 0.088

479
1.4

29.2
5.75 0.16 0.33 2.92 0.18 0.16 0.8
0.11 2.16

50.5

19.3

* Residence time of the gases in the reaction tube.

As can be seen from the examples, by setting the operating temperature in the zones, the catalytic oxychlorination within the preferred temperature range, the conversion of the added chlorinating agent has been successfully maintained within the desired limit, and consequently organic chlorinated hydrocarbons are produced, which mainly consist of unsaturated chlorinated hydrocarbons exist. In addition, the unsaturated chlorinated hydrocarbons formed contain small amounts Amounts of chlorine; there are normally 2 or fewer chlorine atoms in the product unsaturated chlorinated hydrocarbons present.

Claims (3)

Patent claims: 1. Process for the production of unsaturated chlorinated hydrocarbons with 2 to 4 carbon atoms by oxychlorination of the corresponding saturated hydrocarbons with hydrogen chloride or chlorine and an oxygen-containing gas in the presence of metal halides as a catalyst, characterized in that the oxychlorination is carried out at 470 to 55O ⁰ C and a ratio of the catalyst weight (in grams) to the feed rate of the total gases (in liters per minute) from 30 to 120 performs. 10 2. The method according to claim 1, characterized in that there is copper chloride as a catalyst used. 3. The method according to claim 1 and 2, characterized in that the temperature of the catalyst zone is set ^{to 485 to 51O 0 C.} References considered: U.S. Patent Nos. 2,674,633, 1,654,821.