DE1817281A1 - Process for the production of allyl chloride or metallyl chloride - Google Patents

Description

■ PATENT ADVOCATE

DR. E. WIEGAND DIPL-ING. W. NIEMANN 1817281

·. DR. M. KOHLiR DIPL-ING. C. GERNHARDT

MONCHBN HAMBURG TBUFON. 358474. 8000 MUNICH 15, TELIOKAMMBi KARMTBNT '· ■ NUSSBAUMSTRASSE 10

W H 056/68

Showa Denkö Kaiausniki Kaisha. 2okyo, Japan

Yerfahren for the production of allyl chloride Ä

or Methallylchloriä. -

The invention relates to a method of manufacture of allyl chloride or methallyl chloride by reacting propylene or isobutylene with a gas mixture that ' • Contains hydrogen chloride and oxygen, in the presence of an improved catalyst system.

The implementation of. Hydrocarbons, halogenated Hydrocarbons, acidic hydrocarbons en and the like, especially olefinic carbons, with gas mixtures containing hydrogen chloride and oxygen, in the presence of a catalyst " jors forming the corresponding chlorinated pro-cacts, is known as "oxychlorination". The oxychlorination, where hydrogen chloride and oxygen are used as chlorinating agents, has numerous Advantages over conventional chlorination processes, where chlorine is used as a chlorinating agent, for example, that in the former method the cheap one

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and readily available hydrogen chloride can be used, which is why this process has recently become significant Attracted attention.

The oxychlorination of olefinic hydrocarbons can be divided into two categories
by the reaction mechanism, ie addition and substitution chlorination. The production; of allyl chloride or methallyl chloride from propylene
or isobutylene, according to the invention, belongs to the second type, ie to substitution chlorination, such as
from; the following equation gives:

approx

R, .R

= C-CH, + HCl + 1/2 O ₂ Ϊ CH ₂ ». C-CH ₂ Cl + '

t>

wherein R is a hydrogen atom or a methyl group.

It is also known that in general
Above reaction leading to allyl chloride or methallyl chloride, various side reactions occur. Therefore, there has long been a need to develop new catalysts which not only accelerate the reaction rate but also improve the selective conversion of the Ausgarigskohlenwasserstoffes into the desired compound. Among the most preferred catalysts among those proposed so far are tellurium and / or tellurium compounds as catalysts, and combined catalysts that consist of one

# 09833/1487

.- rf. (<iif «in. tr t *

• Component

such tellurium-containing and compounds of alkali metals, Vanadium, molybdenum or tungsten are made. {Japanese published applications 17134/66 and; 19330/66, Belgian patent 70341).

It is assumed that the tellurium or the tellurium compounds in all cases combine with at least one chlorine atom of the reaction zone and therefore the excellent catalytic activity resulted in «However are these well-known catalysts that have a part part included, uselessly one or more exposed to behavior that is detrimental to the industry, for example a reduction in the catalytic properties Activity within a short period of time, low activity and consequently low yield in the Time unit. -.... / "■; -

Demgegenüliosf has now been found that a Kombinat ionskatalysat®% of a) a "Iellurbestandteil and b) a least ens © ¥ © s Msifea§;? Ni ₉ to Pb, Ou, Ag, Pd and Pt erfindungsgemäS contains a © _s. β has or rather high activity and selectivity and continues to maintain these high values for long periods of time. This excellent activity is obtained by an unexpected synergism between the above listed components a) and b).

The object of the invention is ^a a group of nettön catalysts which have high activity and show selectivity over a long period of time in the production of allyl chloride or Methallylchl'orid "by extending substituting oxychlorination of propylene or isobutylene, as well as in a method for the production of allylchlo-

9 Ö 9 8 _{33/1487 0mml lH} 01 * CTED

rid or methallyl chloride "with high effectiveness under, - Use of the new catalysts.

Other objects and advantages of the invention will emerge from the following description.

The above objects are mixed by the inventive method for producing * of allyl chloride and methallyl chloride by expiring under oxychlorination reaction of the corresponding olefinic carbon> ,. · ■■ 'hydrogens propylene and isobutylene with a Gasgefe} the _{hydrochloric%} and contains oxygen in the Vapor phase and at elevated temperature in the presence of a catalyst supported on a carrier, a combination catalyst being used which contains a) at least elemental tellurium or tellurium compounds and b) at least one compound from the group of compounds of Ni, Fb, Cu, Ag, Pd and Pt contains -

The invention is described in detail below. '. ''. .

Elemental tellurium and all known vif compounds can be used as one component of the combination catalyst used in the oxychlorination according to the invention, ie the Teliurbe component. They seem always to _t verbindien with chlorine under the oxychlorination conditions', and show daduroh catalytic activity. Examples of such tellurium compounds include "inorganic tellurium compounds. Fertilizers, such as the oxides, chlorides, oxychlorides, oxyacids and oxyacid salts and organotellurium compounds, for example mono-, dialkyl and -aryl tellurides, alkyl and aryl tellurium trichlorides and dialkyl and di-

; _; 9 Ö 9 8 3 3 / U 8 7 _{0R1G1NAL INS} recTEO

"I.
t -

■ _k t - -t ■

'arylteliuriiehlori & e. For easier handling and for (Wearing the catalytic converter "" is normally used such compounds easily in a suitable inorganic acid are soluble, "for example, the inorganic.! Dellur compounds listed above, ■ preferred *.

The ajidere component of the combination catalyst according to the invention "consists of compounds of metals of group Ii, Pb ₁ Cu, Ig, Pd and Pt. More specific examples of such compounds are oxides, inorganic and organic salas of these metals ^ and to this: belong those oxides _r Ohloride, nitrates, Sui ^ did, phosphates, acetates and propionates of the above metals. "the part of these metal compounds may further contain, in the form of a salt einee. Oxy acid of tellurium is present, which was obtained by chemical reaction / with the tellurium components listed above, for example copper (II) tellurate or ^ -itjellurite.

It was found for the first time that all of them of the above-listed components b in combination with the Eellurium component a an excellent show synergistic effectiveness. This unexpected effect cannot be achieved if other metal compounds, for example of alkali metals or of vanadium, can be used as component b. Farther, is also using component b alone, for example a compound of Cu, Pd or Pt alone, the "object of the invention cannot be achieved. '· -.-.-'.

From. the components listed above "to are copper bonds ^ in particular due to this

ORIGiNAL - (NSPECTlEO

1 J J i J i * > J

r J 4 > * J ■>-> i

J J- - t J i Λ - t

draws that they hone. Activity values during a ι can maintain a much longer period of time than the others. ren metal compounds. Palle a copper compound ale Component b is used, so leave high space » booty in. the unit of time up to 200 g / pc ·! easy obtained for at least 100 consecutive hours.

The combination catalyst can be prepared by supporting the above components a and b in a desired ratio on a carrier. However, if the ratio of the component b is too low, the catalyst life will be shortened. If, on the other hand, e & is too high, addition chlorination, which is an undesirable side reaction, is favored. That's why in the. generally preferred if the ratio of constituent a to constituent b is selected within the range from 1 s 0.1 to 1: 2, given as the atomic ratio of the metals

As a carrier on which the catalyst components are carried Usual porous carriers, for example activated carbon, activated aluminum oxyct, silica-aluminum oxide, silica gel, zeolite, pumice, kaolin and the like can be used. Like. Be used, the best results are achieved with activated carbon. Tinter use of activated carbon, as a bearer, specials can see high kat aly ti ' Activities and selectivities compared to the pail of using other vehicles can be obtained.

The catalyst components can be maintained on the carrier by any known suitable means · The particle size of the supported catalyst may suitably depending on the la The type of catalyst bed used can be selected,

r r

- ■■> '■■ -: - "■' ■■ '■ ■ ■' .- '.;

"For example, bed, fluidized bed or fluidized bed? It is not absolutely necessary to calcine the catalyst in the supported state on the support, but calcination is preferred because of the beneficial effects," for example an improvement in the affinity of the catalyst components for the support, Increase in catalytic activity and the like. Thus, it is recommended to calcine the catalyst at temperatures of 100 to 600 ⁰ O for 1 to 10 hours in an inert gas. The specific temperature and the appropriate time must be appropriate depending on the Types of Catalyst Ingredients and Volatility of the Ingredients to Be Chosen The amount of the ingredients on the support is not critical, but it is usually preferred that the catalyst on the support be about 1 to 30% by weight. CelluaEfcesta & Ateils, based on the metal, contains *. .

The oxychlorination for the lower substitution of! propylene or isobutylene according to the invention the reaction conditions to be used are fundamental the same as they are used in conventional oxy chlorinations proceeding with substitution, it is however, the combination catalyst listed above uses the preferred practical embodiment of the present procedure is as follows:

All of the compounds, propylene or isobutylene, Hydrogen chloride and oxygen, which are used as starting materials can be used with suitable chemically inert substances under the reaction conditions

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ORIGINAL INSPECTED. 'Γ

conditions, for example lower saturated hydrocarbons such as ethane, propane and butane, nitrogen, Carbon dioxide, noble gases, water vapor and the like * diluted will. Therefore, oxygen can be in the form of air and hydrogen chloride in the form of evaporated hydrochloric acid be set. The quantitative proportions of the starting constituents to be supplied to the reaction zone can represent the stoichiometric ratio * required for substitution chlorination. On the other hand it is preferred if one or two components of the three used in excess of the order of magnitude from the. 1.5 to three times the stoichiometric amount are present in order to form an explosive To prevent composition or to facilitate the implementation of the implementation.

ITm both conversion of the starting olefin and the selectivity of the Substitutionschlo> turing to maintain at the desired high levels, reaction temperatures in the range of 100 to 400 ° 0, are preferred from 150 to 35O ⁰ C, in particular 180 to 25O ⁰ C is Wandt. The preferred reaction pressure can be between 1 and 30 atm. The suitable space velocity of the gas supply at such a reaction temperature and such pressures is about 500 to 3000 " ¹ (Η.Ϊ.Ρ.)

As can be seen from the above explanations, the method according to the invention produces a steam phase reaction. The catalyst can be used in a plague bed, in a fluidized bed or in a fluidized bed ·

The reaction conditions listed above are not critical features of the invention

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'but may be suitable for industrial practice Way to be changed or modified.

The invention is explained below with the aid of working examples. Palis not stated otherwise parts are by weight and parts by volume "mean the fourth, that with the relationship of volume parts in cubic centimeters and parts by weight in grams. .

The yield of the products allyl chloride or methallyl chloride was "determined by the gaseous Reaction mixture was subjected to gas chromatography β Also the conversion in the implementation ^ e -samg- was the amount of unconverted hydrogen chloride determined that in an alkaline aqueous. Solution was collected when the gaseous reaction mixture it was introduced-,

• · ' Example 1 "

. 1.5 l of tellurium oxide and 0.3 ropes of copper (II) chloride dihydrate were dissolved in hydrochloric acid. 30 volumes Activated carbon corresponding to a number of meshes / cm / From 16 "■ '

/ were immersed in the "solution and the solution evaporated, the dry solid catalyst was obtained, which was then ^{calcined at 400 0} C for 5 hours under nitrogen *

A tubular reaction vessel with an internal diameter of 18 mm was charged with 20 cm of the catalyst obtained in this way and! in this a gas mixture from 30 volumes of propylene, 20 volumes of hydrogen chloride, 10 vol .- # oxygen and 40 vol .- ^ nitrogen

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at a tree speed of 1000 hours at 20O ⁰ C and atmospheric pressure. During the reaction, allyl chloride was obtained in an amount of 7.6 g per hour. The hydrogen chloride conversion was 70 and the selectivity for allyl chloride was 60. No decrease in the catalyxic activity was observed even several hours after the start of the reaction, and it was found that the catalyst could be used satisfactorily for much longer periods of time.

comparison

Example 1 was repeated, but using copper (II) chloride as one of the catalyst components omitted. Immediately after the start of the reaction, allyl chloride was added in an amount of 7 g / h. educated, however, the decrease in catalytic activity with the lapse of time was remarkable. Four hours after it started the rate of formation of allyl chloride was only 4.3 g / h. ·

Example 2

One part tellurium oxide and 1 part copper (II) chloride dihydrate were dissolved in hydrochloric acid and 20 parts by volume of activated carbon corresponding to a Kaschen number / cm-ναχ1δ ( 10 mesh) immersed. The solution was then evaporated to dryness. 20 cm of on this Catalyst dried in this way were introduced into a tubular reaction vessel and a gas

90983371487

Mixture of 30 vol .- # propylene, 20 vol .- # hydrogen chloride, 10 vol .- 56 oxygen and 40 YoI. -i> nitrogen at a space velocity of 1000 St. "at 210 ^° C. and atmospheric pressure. During the reaction, allyl chloride was added in an amount of 6.0 g / hour, isopropyl chloride in an amount of 0.7 g / hour, and Propylene dichloride in a quantity of 1.1 g / St ".

Example 3 '

Example 2 was repeated, but using silica gel as the catalyst support. Allyl chloride was in an amount of 2.4 g / St, and isopropyl chloride in one Amount of 2.5 g / pc. Seven hours after it started the conversion "was the reduction in catalytic Activity less than

'. Example 4

Example 2 was repeated, but silica-aluminum oxide (Aluminum oxide = 13 $) all catalyst supports used. Immediately after implementation begins were 3.0 g / pc. Allyl chloride and 4.0 g / st, isopropyl chloride educated. The catalytic activity. was on after 7 hours from the start of the implementation Half decreased.

Example 5
A portion of sodium tellurite was dissolved in water

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and immersed therein 20 parts by volume activated carbon. Immediately after the addition of 1.1 ropes of copper-II-nitrate-trihydrate, green copper-II-itellurite. The precipitate was washed with water and the liquid evaporated off * The catalyst thereby obtained was for 1 hour in nitrogen at 200 ⁰ C allowed to itehen. '> Using this catalyst, the O described in Example 1 has been carried out xychlorierung, but the Reaktionetemper & tur USi changed 215 ⁰ C. Allyl chloride was formed in an amount of 5.5 g / hour. The. Response Rate Remained $ 0 hours after the start of the conversion; unchanged. The hydrogen chloride conversion was 60 ° C. and the selectivity to allyl chloride was 65 °. ^f -

i _# t. aieile, tellurium tetra chloride and ^; 1 rope of Kupfeac-II-nitrate - * - | rihy.drat. Were dissolved in hydrochloric acid and ^{immersed in the i 20 parts by volume of activated carbon corresponding to a 2} j; /. Then became

The air evaporated from the dryness; The thereby-obtained catalyst was kalEiniert .400 at ⁰ C for 4 hours in Stiokitoff. It was oxychlorination carried out as in Example 1 using this calcined catalyst 1> ei 215 ⁰ C. Allyl chloride was obtained in an amount of 4 »5 g / st · after two hours of reaction, 4.5 g / st» after ten hours of reaction and 4 »6 g / st * after 20 hours of reaction»

r-

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ORITSTNALiNSPECTEO

- 13 - 1817201

Example 7

0.72 part of tellurium oxide and 0.77 part of cupric chloride dihydrate were dissolved in hydrochloric acid and 20 volumes

• Mental activated carbon corresponding to a mesh number / cm of (10 mesh) is immersed therein. The solution was then evaporated to dryness. The dried catalyst was then "at .400 ⁰ G for 4 hours in nitrogen

. calcined. '

Using the catalyst thus obtained the oxychlorination wurde- carried out as in Example 1 but keeping the reaction temperature at 215 ⁰ C. "The formation of allyl chloride in the course of time, altered only slightly, as can be seen from the following table, which practically constant and sustained activity of the catalyst proves:

4 hours after the start of the reaction 3.6 g / h.

20th Il Il t
Example 8 It i 3.5 g / st. 40 Il Il Il 4.0 g / st. 60 η r Il Il. 3.7 g / st. 100 Il It . »I. 3.6 g / st.

One part of tellurium oxide and 1.2 parts of copper (II) sulfa-fep.entahydrate were dissolved in hydrochloric acid and 20 parts by volume of activated carbon corresponding to a mesh number / cm of (to mesh) immersed in it. The solution then became

ORDINAL INSPECTED 909 83 3/14 87

Dry evaporated. The dry festei catalyst thus obtained was calcined at 400 ⁰ C for 4 hours in nitrogen. Dia oxychlorination was in the same manner as in Example 1 using this catalyst, and a gas mixture of 30 vol .- # isobutylene, 20 vol .- # hydrogen chloride, oxygen and 10 vol .- # 40 .- ^ VoI nitrogen at 215 ⁰ C executed.

Methallyl chloride was used in an amount of -7-g / St, educated.

• ' Example 9

Ea a catalyst was produced with the same composition as in Example 6, which was then ^{reduced in a hydrogen stream of 200 °} C. for 2 hours and not ^{calcined at 400 °} C. for 4 hours in nitrogen. The catalyst obtained in this way was used in the oxychlorination described in Example 6 and gave practically the same result.

Example 10

1.8 parts of telluartetrachloride were dissolved in acetic acid solved. Thirty parts by volume of activated carbon accordingly a mesh / cm νααΪ6 (10 mesh) became the solution added and held therein for 1 hour. The acetic acid was then evaporated. The ΐ-ellur Traditional activated charcoal was then dissolved in an acetic acid solution immersed, the 1.4 parts of copper (II) acetate mono-

_nnn ORIGINAL! HSFECTED

9 0983 3 / U87

hydrate contained, left to stand for 12 hours and the Plüe- ^! evaporation. ■

The obtained catalyst was used in oxychlorination OCE according to Example 1 at a Reaktionsgemperatur of 20O ⁰ C. 6.5 g / pc. Allyl chloride obtained and no sign of a decrease in catalytic activity was observed after 20 hours of reaction,

Example 11

1.5 parts of ffelluroxide and 1.3 parts of lead acetate trihydrate nitric acid was dissolved and "0 parts by volume Shares corresponding to a Maeoh number of 15 (10 mesh) in the same way as in the catalyst production naok Bdifepi @ l 1 b @ acts.

• When using βββ. © s> hold © a catalyst for oxy » chlorieiiiifcg ηβ-Oh. 'Betipial 1 was 7 g / St * AlXylehlorl formed Md 20 hours. at the beginning of the ümsetaimg were always nooh 5 * 3 g / ßt »AXlylohloriS formed.

ii '· - "■' ■ · ·

12 / ■.

holds down, but lead acetate

■ 6 ·! ümn b ± m. »* tkm tMZ & UQhm. as a catalyst bed part 3urea Silfe @ Äit ^ at _s Hiokelehlarid and Palladiuaohlorid

In 'feMmtllö ^ m Fällsa the ealalyeators soaped

Iche ÄrlsßSiikeitea WiQ ö®s totalizator naoh example 11: ο

· ORIGINAL INSPECTED

Claims (10)

Claims Contains 1. A process for the production of allyl chloride or methallyl chloride by oxychlorination of the corresponding olefinic hydrocarbons propylene and isobutylene with a gas mixture containing hydrogen chloride and oxygen in the vapor phase and at elevated temperature in the presence of a catalyst supported on a carrier, characterized in that a Kombinationskatalysatox containing a) elemental tellurium and / or tellurium compounds and to-) 'at least one compound of Ki, Pb, Gu, Ag, Pd or Pt is used. 2. Procedure according to. Claim 1, characterized in that a catalyst is used whose ratio of constituent a to constituent to. in the range from · 1 ί 0.1 to 1 i 2, given as the atomic ratio of the metals. 3 ·· Method according to claim 1 or 2, characterized in that . indicates that a catalyst is used whose carrier consists of activated carbon. 4. The method according to claim 1 to 3, characterized in that a catalyst is used whose component la consists of copper compounds and -. "· '. ORIGINALINSPECTED 909833 / 1A87 '* 17 - is mti , - 2 2rag3? made of activated carbon ΤιββΐβΜ. 5 · 'method / according to claim 1 "to 3, marked by -. Characterized that EIA combination catalyst composed of the copper salt, a Öxysäure tellurium" is used' is. ■ ■,. "'- -.'" : '[-' ■ ■■ '/ ..''. ■ '. 6 ». A method according to claim 4 characterized gekennzeioh- _f · net. because the component fr consists of copper chloride. 7., procedure according to. Claim 4, characterized in that the seat part "b consists of copper nitrate". 8. The method according to claim 4j, characterized . that the sea component fr consists of copper sulfite. 9, method according to claim 4 » , characterized in that the component b consists of copper acetate. 10. The method nach'Anspruch 1 to 9 characterized labeled in _t characterized in that a supported catalyst on the carrier, which at 100 to 600 ⁰ C while: is calcined for 1 to 10 hours> iurde used. '. • S 11 ». Process according to Claims 1 to 10, characterized in that a reaction temperature in the range from TOO to 400 ⁰ O and a reaction pressure between 1 and 30 atm are used. ■ *