DE1228598B - Process for the production of 1, 2-dichloroethane - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C07c

German class: 12 ο -2/01

Number: 1228 598

File number: D 38556IV b / 12 ο

Filing date: April 2, 1962

Opening day: November 17, 1966

The chlorination of hydrocarbons by reaction with hydrogen chloride and oxygen in the Vapor phase at elevated temperature in the presence of copper (II) chloride, which is made on a fixed bed inert carrier material is applied, as a catalyst is known. According to the invention, for the Oxychlorination of ethylene used an improved catalyst.

The invention relates to a method for preparing 1,2-dichloroethane by reacting ethylene with hydrogen chloride and oxygen in the presence of applied one on a support, the copper-containing catalyst at elevated temperatures, characterized in that the reaction at 225-500 ⁰ C. executes and uses a catalytic converter that has been produced by the following measures:

a) heating (at least 2 hours, up to 24 hours) of commercially available activated aluminum oxide to 600 to 1400 ^° C .;

b) impregnation with an aqueous cupric chloride solution and drying, or impregnation with an aqueous solution of a copper salt and drying under conversion of ^a 5 used in the copper salt of copper, wherein the dry catalyst in each case contains from 0.5 to 5 weight percent copper.

It has been found that by using such a heat-treated alumina as a catalyst carrier reduces the amount of carbon dioxide present in the reaction products and the yield of the desired chlorinated hydrocarbons is increased significantly.

The aluminum oxide can be impregnated with a copper chloride solution immediately after the heat treatment, dried and used as such in the reactor. It is also possible to use the alumina with a solution of a copper salt, e.g. B. the nitrate or formate to impregnate, which is then in the pores of the aluminum oxide by thermal decomposition during the subsequent drying in Copper oxide is converted.

According to a particular embodiment of the invention, the catalyst can also be an alkali salt included as an activator. The alkali salt is used in such an amount that it is 0.5 to 5% by weight of the finished catalyst, calculated as an alkali metal.

The alkali salt is made by impregnating the aluminum oxide with a solution of the alkali salt
1,2-dichloroethane

Applicant:

The Distillers Company Limited,
Edinburgh (Great Britain)

Representative:

Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald,
Dr.-Ing. Th. Meyer and Dr. JE Fues,
Patent attorneys, Cologne 1, Deichmannhaus

Named as inventor:

Clifford William Capp, Ewell, Surrey;

David James Hadley, Epsom Downs, Surrey;

Patricia Eileen Waight,

Sutton, Surrey (UK)

Claimed priority:

Great Britain April 25, 1961 (14 836),

dated September 6, 1961

(31 949),

dated November 10, 1961

(40251),

dated January 8, 1962 (671)

incorporated into the catalyst before or after the heat treatment. The impregnation can take place before, after or during the application of the copper. Suitable alkali salts are the hydroxides, chlorides, carbonates, aluminates and / or nitrates. Organic salts such as formates, oxalates and / or acetates can also be used. The catalyst can contain several alkali salts. Sodium and chewing salts are preferably used. Potassium salts are particularly preferred.
According to a further embodiment of the invention, the alkali-activated catalyst can also contain salts of iron or of rare earths. It has been found that the presence of these salts reduces the volatility of the copper contained in the catalyst. The term “rare earths” includes elements with ordinal numbers 57 to 71. These include cerium, lanthanum and neodymium, for example. The iron salt or the

609 727/430

3 4

Rare earth salt is used in an amount of 0.2. For comparison, that described above up to 10 percent by weight, based on the catalyst experiment repeated, the catalyst used being a copper carrier and the alkali salt. chloride on activated aluminum oxide, which none

The iron salt or the rare earth salt has been subjected to heat treatment, and

incorporated into the catalyst, before, after. or 5 a reaction temperature of 301 ⁰ C applied

during the incorporation of the activator. The maximum conversion of hydrogen chloride

Alkali salt by impregnation of the aluminum to chlorinated products was only 17.3% that up

oxyds with a solution of the desired iron salt reacted ethylene-related carbon dioxide formation

or salt of the rare earth, before or after the 6 ° / ₀ .

Heat treatment. As iron salts or salts, less often io example2
Hydroxides, chlorides and carbonates can earth

and nitrates can be used. Organic salts, according to the invention, have also been used such as formates, oxalates and acetates, the catalyst described in Example 1 and can be used will. The catalyst can have several iron salts reactor ethylene (5000 parts by volume / hour), chlorine or. Contains rare earth salts. 15 hydrogen (10,000 parts by volume / hour) and air (12,500

To carry out the process, the carrier parts by volume / hour) can be mixed and carried out at 324 ° C

catalyst passed as a fixed bed in the form of tablets or 200 parts by weight of catalyst,

as granules or as a fluidized bed or fluidized bed The conversion 'of hydrogen chloride to chlorinated

can be used. Products was 63% Ke yield of 1,2-dichloro

The quantitative proportions of the reactants 20 ethane was 61.2%, based on the chlorine used

essentially the stoichiome hydrogen can be used. The yield of vinyl chloride was around

trical requirements of the reaction carried out 0.76%

correspond. In practice, however, it may be desirable for example3
be to use the alkylene and / or the oxygen in excess in order to achieve maximum conversion for the product. The oxygen in use can ■ in the manner described in Example 1 from 95 weight diameters ■ any suitable gases containing molecular parts of commercially available activated aluminum oxide oxygen: z. B. air, are supplied. that was kept at 1100 ° C for 22 hours. As in Example 1, the reactants were mixed by using ethylene (6900 parts by volume / hour), hydrogen chloride of pure, undiluted molecular oxygen (15,400 parts by volume / hour) and air (18,900 parts by volume / hour). ) passed through the reactor at 336 ° C.

The contact time can be 0.1 to 30 seconds. The conversion of hydrogen chloride to chlorinated

and is preferably between about 5 and 15 seconds. Products was 64.7%; the yield of 1,2-di-

the. 35 chloroethane, based on the hydrogen chloride used,

The hydrogen chloride can be in any suitable position at 62.3%

Shape, e.g. B. as a waste product that is produced in Example 4
of vinyl chloride by pyrolysis of 1,2-dichloro

Ethane accruing should be imported. A catalyst was made by diluting 100% its or partially replaced by chlorine 40 parts by weight of commercially available activated aluminum, oxide, which was present in the form of fine globules and before

In the following examples, 24 hours by weight were heated at 1100 ° C. to one

divide to parts by volume as grams to cubic centimeters. Solution of 4.3 parts by weight of copper (II) chloride in

The percent yields are on a molar basis given to 100 parts by weight of water. the

specified. 45 Mixture dried to dryness with constant stirring

η · · 1 1 evaporated and dried for ^{6 hours at 12O 0 C,}

P whereupon it contained 2 weight percent copper. That

A catalyst was prepared by adding a 100 g mixture of catalyst and support

parts by weight of commercially available activated aluminum oxide impregnated with an aqueous sodium chloride solution

(Particle size 75 to 150 μ), which was previously 50 and dried for 24 hours. This made 3 percent by weight

had been heated to 1000 ⁰ C, incorporated into a solution of sodium chloride.

4.3 parts by weight of copper (II) chloride in 100 parts by weight of ethylene (7500 parts by volume / hour), parts of hydrogen chloride were given water. The mixture was (15,000 parts by volume / hr.) And air (18 750 Volumunter constant stirring evaporated to dryness parts / hr.) Were mixed and dried down in one and 6 hours at 12O ⁰ C, whereupon it 55 fluidized bed at 350 ⁰ C contained in one with a constant 2 weight percent copper. Temperature-held reactor arranged catalyst

Ethylene (7500 parts by volume / hour), hydrogen chloride sator passed. The yield of 1,2-dichloroethane (15,000 parts by volume / hour) and air (18,800 parts by volume was 51.7%, based on hydrogen chloride parts / hour) were mixed and used for comparison over the catalyst the above experiment was also carried out, which ^{repeated my fluidized bed at 303 °} C. in a catalyst of the same type, but which in this case did not contain any alkali metal salt in the reactor kept at the same temperature. Which was adhered to. The maximum conversion of hydrogen chloride-based yield of hydrogen chloride to chlorinated products was 53%. 1,2-dichloroethane was only 32.3%.

The yield of 1,2-dichloroethane was 95.6%. .

based on converted ethylene, the yield of 65 Example 5

Vinyl chloride 2% and carbon dioxide formation 1.4%. A catalyst / support mixture was applied to the im

The manner described from Example 4, based on the hydrogen chloride used, was prepared and used

The yield of 1,2-dichloroethane was 51.75% · 1.5% by weight of sodium chloride impregnated.

Ethylene (7500 parts by volume / hr.), Hydrogen chloride (15 300 parts by volume / hr.) And air (18 780 parts by volume / hr.) Were mixed and passed over the ⁰ C held in the fluidized bed at 35O catalyst in a room kept at constant temperature reactor . The yield of 1,2-dichloroethane was 59.2%, based on the hydrogen chloride used.

Example 6

IQ

100 parts by weight of commercially available activated alumina in the form of fine beads which previously 24 hours on HOO ⁰ C had been heated, was added water to a solution of 4.3 parts of copper (II) chloride and 1.15 parts of potassium chloride in 100 parts. The mixture was evaporated under constant stirring to dryness and dried for 6 hours at 12O ⁰ C, after which they contained 2 parts by weight of copper and 0.6% potassium.

Ethylene (7500 parts by volume / hr.), Hydrogen chloride (15,900 parts by volume / hr.) And air (18 000 parts by volume / hr.) Were mixed and passed through 120 parts by volume of the catalyst as a fluidized bed of 303 ⁰ C in a at a constant temperature held reactor was used. The 1,2-dichloroethane yield was 69%, based on the hydrogen chloride used. When the potassium chloride content was increased to 1.15%, the yield rose to 76.1% under the same reaction conditions.

B e i s ρ i e 1 7

A catalyst was prepared in the manner described in Example 6, adding 4.3 parts Copper (II) chloride and 1.15 parts of potassium chloride to 100 parts of commercially available activated aluminum, which was in the form of fine beads and had previously been heated to 1100 ° C, were given.

Ethylene (7520 parts by volume / hr.), Hydrogen chloride (16180 parts by volume / hr.) And air 8850 parts by volume / hr.) Were passed through 120 parts by volume of the catalyst which was used as a fluidized bed of 303 ⁰ C. The 1,2-dichloroethane yield was 76.1%, based on the hydrogen chloride used.

Example8

A catalyst was prepared by adding 100 parts of commercially available aluminum oxide (grain size 0.85 to 2 mm) to a solution of 1.78 parts by weight of potassium carbonate in 50 parts of water. The mixture was evaporated to dryness and heated to 1060 ° C for 24 hours. A solution of 4.3 parts of copper (II) chloride in 100 parts of water was added to the mixture which was then evaporated to dryness with constant stirring and 6 hours at 12O ⁰ C was dried. The catalyst now contained 0.5 percent by weight potassium and 2.0 percent by weight copper.

Ethylene (1760 parts by volume / hr.), Hydrogen chloride (3200 parts by volume / hr.) And air (8000 parts by volume / hr.) Were mixed and passed at 302 ⁰ C over the catalyst (36 parts by volume) in an isothermal fixed-bed reactor. The maximum conversion of hydrogen chloride to chlorinated products was 99.2%.

Example9

A catalyst was prepared by adding 100 parts of a commercially available activated aluminum oxide consisting of fine spheres (particle size 75 to 150 μ), which had previously been ^{heated to 1060 °} C. for 24 hours, to a solution of 2.3 parts of potassium chloride, 3.1 Parts of copper (I) chloride and 5.0 parts of iron (III) chloride were added to water. The mixture was evaporated to dryness with constant stirring and ^{dried at HO 0} C for 6 hours, whereupon it contained 2% copper, 1.2% potassium and 1.7% iron.

Ethylene (10,200 parts by volume / hr.), Hydrogen chloride (19,500 parts by volume / hr.) And air (24 300 parts by volume / hr.) Were mixed and passed through the catalyst in an amount of 120 parts by volume of the fluidized bed at 301 ⁰ C was placed in a reactor maintained at a constant temperature.

The maximum conversion of hydrogen chloride to chlorinated products was 85.5%. About 98% of the hydrogen chloride used were obtained as 1,2-dichloroethane.

Example 10

278 parts of an activated aluminum oxide consisting of fine spheres (particle size 75 to 150 μm) were added to a solution of 2.46 parts of potassium carbonate in water. The mixture was evaporated to dryness with constant stirring and then heated ^{to 1060 ° C. for 24 hours.} It was then added to a solution of 15.8 parts of cupric chloride dihydrate and 3.52 parts of technical grade cerium chloride in water. (Technical cerium chloride is obtained from a mixture of lanthanides contained in monazite, which has the following approximate composition: La ₂ O ₃ 23%> CeO ₂ 35%, Pr ₆ O ₁₁ 6%, Nd ₂ O ₃ 18%, Sm ₂ O ₃ 3%, other lanthanides 5% ·) The mixture was evaporated to dryness with constant stirring and ^{dried for 6 hours at 110 °} C., whereupon it contained 2% copper, 0.5% potassium and 2% lanthanides.

Ethylene (2500 parts by volume / hour), hydrogen chloride (4950 parts by volume / hour), oxygen (1200 parts by volume / hour) and nitrogen (32,900 parts by volume / hour) were mixed and passed through the catalyst (120 parts by volume), which in a fluidized bed was kept at 300 ⁰ C. 86.5% of the hydrogen chloride was converted into 1,2-dichloroethane and 7.5% of the ethylene was burned.

Example 11

A catalyst was produced in the manner described in Example 10, but ^{aluminum oxide, previously heated to 1060 °} C. and having a grain size of 0.85 to 2 mm, was used as the support. Ethylene (3030 parts by volume / hr.), Hydrogen chloride (5880 parts by volume / hr.) And air (7700 parts by volume / hr.) Were passed through the catalyst (36 parts by volume) at 300 ⁰ C, which as a fixed bed in a room kept at constant temperature reactor was arranged. 98.1% of the supplied hydrogen chloride was converted into 1,2-dichloroethane and only 1.3% of the ethylene was burned.

Example 12

Ethylene (2650 parts by volume / hour), hydrogen chloride (5000 parts by volume), oxygen (1365 parts by volume / hour) and nitrogen (32 735 parts by volume / hour) were

mixed and passed through the catalyst of Example 11 (120 parts by volume) kept in a fluidized bed at 30O ^{0 C.} Here 95.2% of the hydrogen chloride were converted to 1.2% dichloroethane and 1.9% of the ethylene was burned to form carbon dioxide.

Example 13

There are various catalysts by the addition of 100 parts by weight of aluminum oxide to a solution of 10.74 parts by weight Cuprichloriddihydrat, 1.147 parts by weight of potassium chloride and 10 _s 14 parts by weight Thoriumnitrathexahydrat dissolved in 200 parts by weight of water was prepared. The mixtures were evaporated to dryness with constant stirring and at 12O ⁰ C for 6 hours

dried. They then contained 4% copper, 0.6% potassium and 4% thorium. The aluminum oxide used was treated at 680, 900, 1000 and 1060 ^° C. for 24 hours before the impregnation.

Ethylene (2450 parts by volume / hour), hydrogen chloride (4660 parts by volume / hour) and air (5850 parts by volume / hour) were mixed and passed over the catalyst, which comprised 36 parts by volume as a fixed bed in an isothermal reactor.

The conversion of hydrogen chloride was measured over a range of temperatures. The table below clearly shows when the complete conversion is achieved, namely at temperatures for the pretreatment of the aluminum oxide above 68O ⁰ C.

Tem 200 ⁰ C Conversion before 220 ° C ι HCl in ° / , related ί 240 ° C 250 ° C 26O ⁰ C 270 ° C 280 ⁰ C 290 ° C 300 ° C temperature 73.4 93.2 90.2 86.2 64.5 the
Heat heave 55.0 99.8 96.4 91.2 90.8 88.8 84.0 81.2 76.6 plot 210 ⁰ C 81.1 98.7 96.4 95.5 94.8 90.4 86.0 ° C 90.5 97.9 97.5 680 900 iuf the hydrogen chloride fed to the reactor 1000 at the specified reaction temperatures 1060 230 ° C 90.4 98.4

Claims (7)

Patent claims: 1. A process for the preparation of 1,2-dichloroethane by reacting ethylene with hydrogen chloride and oxygen in the presence of a supported, copper-containing catalyst at elevated temperatures, characterized in that the reaction is carried out at 225 to 500 ⁰ C and a Catalyst is used, which has been produced by the following measures: a) heating (at least 2 hours, up to 24 hours) of commercially available activated aluminum oxide to 600 to 1400 ^° C .; b) Impregnation with an aqueous copper chloride solution and drying or impregnation with an aqueous solution of a copper salt and drying to convert of the copper salt used in copper oxide, the dry catalyst in each case 0.5 to 5 percent by weight copper contains. 2. The method according to claim 1, characterized in that the preheated alumina to Temperäturen between 800 and 1100 ⁰ C. 3. Process according to Claims 1 and 2, characterized in that the conversion into the Copper oxide only makes during the oxychlorination. 4. Process according to Claims 1 to 3, characterized in that the aluminum oxide carrier before or after the heat treatment impregnated with a solution of an alkali salt, wherein the dry, finished catalyst contains 0.5 to 5 percent by weight alkali metal. 5. The method according to claim 4, characterized in that the impregnation of the aluminum oxide with the alkali salt solution before, after or simultaneously with the application of the copper catalyst undertakes. 6. The method according to claims 4 and 5, characterized in that the aluminum oxide carrier before or after heat treatment with a solution of ferrous or rare earth metal salts (Ordinal number 57 to 71) impregnated, preferably at the same time as the impregnation with the alkali salt solution, the dry, finished catalyst 0.2 to 10 percent by weight Contains iron or rare earth metals. 7. Process according to Claims 1 to 6, characterized in that the oxychlorination is carried out within 0.1 to 30 seconds. «09 727/430 11. 66 © Bundesdruckerei Berlin