US2207070A - Process of converting compounds of the acetylene series into compounds of the ethylene series - Google Patents

Process of converting compounds of the acetylene series into compounds of the ethylene series Download PDF

Info

Publication number
US2207070A
US2207070A US193296A US19329638A US2207070A US 2207070 A US2207070 A US 2207070A US 193296 A US193296 A US 193296A US 19329638 A US19329638 A US 19329638A US 2207070 A US2207070 A US 2207070A
Authority
US
United States
Prior art keywords
compounds
zinc
acetylene
series
grams
Prior art date
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.)
Expired - Lifetime
Application number
US193296A
Inventor
Reppe Walter
Rothhaas Alexander
Schmidt Otto
Luehdemann Rolf
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.)
Jasco Inc
Original Assignee
Jasco Inc
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.)
Filing date
Publication date
Priority to DE2207070X priority Critical
Application filed by Jasco Inc filed Critical Jasco Inc
Application granted granted Critical
Publication of US2207070A publication Critical patent/US2207070A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds

Description

Patented July 9, 1940 UNITED STATES PATENT orrlcs PROCESS OF CONVERTING COMPOUNDS OF THE ACETYLENE SERIES INTO COM- POUNDS OF THE ETHYLENE saunas Louisiana No Drawing. Application March 1. 1938. Serial No. 193,296. In Germany March 24, 1937 6 Claims.
The present invention relates to a process of converting compounds of the acetylene series into compounds of the ethylene series.
It has already been proposed to convert acetylene derivatives into ethylene derivatives by treating them with aqueous suspensions of zinc dust to which copper sulphate solution'has been added. The zinc activated by precipitated copper thus reacts with water with the formation of hydrogen. This process has the objection that the hydrogenation proper requires a multiple of the calculated-amount of zinc because on the one hand the reaction proceeds incompletely and on the other hand a considerable part of the zinc is used up by the activation. passing into solution as zinc sulphate. and is thus consumed without being used for the hydrogenation. In order to obtain a satisfactory utilisation of zinc, about one third of the zinc must be replaced by copper.
We have now found that compounds of the acetylene series can be converted into compounds of the ethylene series in a considerably simpler and more advantageous manner by treating compounds 01' the acetylene series in aqueous alkaline solution with metallic zinc, preferably in fine dispersion, as it is obtained, for example, in the electrolytic production of zinc. There may also be added as activators metals capable of forming galvanic elements with the zinc. v
Contrary to expectation, only relatively small amounts of free hydrogen are formed in the hydrogenation by the present process, so that the utilisation of the zinc is very favorable.
' Moreover, the hydrogenation of the acetylene linkage proceeds only to the formation of the ethylene linkage without any appreciable formation of the corresponding saturated compounds.
Even when acetylene compounds which contain olefinic double linkages in addition to the triple linkages are hydrogenated. the hydrogenation is limited to the triple linkages. The present invention, therefore. can most advantageously be r used for the conversion of vinylacetylene into butadiene.
Among suitable activating metals which are capable of forming galvanic elements with zinc there may be mentioned for examplecopper,
50 manganese. iron, cobalt and nickel. The addition necessary for the activation is usually very small. It can be established without trouble by a simple preliminary experiment which combination is most suitable for the hydrogenation to be carried out. In most cases, the addition or an activating metal can entirelybe dispensed with.
The hydrogenation may be so conducted that the zinc passes completely into solution as zincate during the course of the process, by using the alkaline reacting substance in such an amount that the zinc hydroxide formed can be dissolved to form a zincate. It is possible to effect the regeneration of the zinc by electrolysis of these zincate solutions because in this way the zinc is obtained in so finely divided a form that it is suitable for direct re-use without further treatment. 'In many cases. for example in the production of butadiene from vinylacetylene, it is preferable to employ smaller amouniis'of the alkaline reacting substance than are thc0retically necessary for the formation of zincate. At the end of the hydrogenation the zinc employed is mainly obtained in the form of a zinc hydroxide suspension: After having filtered off the zinc hydroxide from this suspension, the filtrate may be used forthe preparation of iresh'zinc suspensions without further purification.
For the preparation of the aqueous alkaline solutions there may be used metal oxides and hydroxides which dissolve in water with an al= kaline reaction. The caustic alkalies sodium and potassium hydroxide are especially suitable. They may be used in various concentrations, for example in 20 per cent solutions, or preferably in from 4 to 6 per cent solutions. The reaction may, however. also be carried out with solutions of alkaline earth hydroxides. If desired, organic solvents which have a good solvent power for the acetylene compounds and which are not attacked under the reaction conditions may be added to the aqueous solutions, as for example aliphatic alcohols. The hydrogenation. may also be carried out in the presence of indifferent substances, as for example indifferent gases. It is often advantageous to work in the presence of dispersing or wetting substances. for example of alkyl naphthalene 'sulphonic alkali salts or the addition products of 20 molecular proportions of ethylene oxide to fatty alcohols of high molecular weight, in order to produce the most intimate possible contact between all the reactants.
Generally speaking it is sufiicient to work at atmospheric pressure and at ordinary or slightly elevated temperature, but any other pressures may be used within a wide range of temperatures.
The process may be carried out continuously. discontinuously or in a cycle. For example con tinuous operation may be effected by adding zinc dust and caustic soda solution at the upper end of the reaction tower provided with difierent rapid stirrers arranged one above another, continuously withdrawing the zinc hydroxide suspension or the zincate solution at the lower end, the gaseous acetylene compounds being led in at the lower end of the tower and the hydrogenation products withdrawn at the upper end.
The process according to this invention may be used for practically all compounds having triple carbon linkages, as for example for acetylene, phenylacetylene, vinyl acetylene, diacetylene, divinylacetylene, methylbutinol, propiolic acid, phenylpropiolic acid and many other acetylene derivatives.
The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples.
' Example 1 Gaseous vinyl acetylene is led at ordinary temperature through a well stirred suspension of 500 grams of zinc dust in a solution of 300 grams of caustic soda in 3 liters of water at such a speed that the throughput is about 20 liters per hour. 15 grams of finely powdered iron are added in small batches during the course of the reaction. The gases escaping from the reaction solution are liquefied by cooling. The reaction is completed when large amounts of unchanged vinylacetylene appear in the final gas. There is thus obtained mainly butadiene which contains only traces of butylene, very little hydrogen and no butane at all.
Example 2 From 10 to 20 liters of acetylene are led during an hour through a well stirred suspension of 500 grams of a zinc dust obtained by electrolysis, 5 grams of iron powder and 2 grams of the condensation product of 1 molecular proportion of oleyl alcohol and 20 molecular proportions of ethylene oxide in a solution of 600 grams of sodium hydroxide in 3 liters of water. From time to time small amounts of iron powder are added. The effluent gases contain, in addition to the ethylene formed, acetylene and small amounts of hydrogen but practically no ethane.
The unconverted acetylene may be again brought into contact with the solution, if desired in a cycle.
. Example 3 2.5 liters of vinylacetylene are shaken in a shaking vessel with-a suspension of 50 grams oi. zinc dust (85 per cent obtained by electrolysis) and 1 gram of butylnaphthalene sulphonic acid sodium salt in 200 cubic centimeters of 20 per cent caustic soda solution for 20 hours at about 20 C. The final gas consists mainly of butadiene with which are mixed a little vinylacetylene and hydrogen and only traces of butylene.
If 3 liters of vinylacetylene be shaken in a flask with a mixture of 50 grams of zinc dust (85 per cent, obtained by electrolysis), 3 grams of iron powder, 3'7 grams of calcium hydroxide, 1 gram of butylnaphthalene sulphonic acid sodium salt and 200 cubic centimeters of water for several hours, the vinylacetylene is also almost completely hydrogenated to butadiene. The final gas contains only traces of butylene and varying amounts of hydrogen.
The hydrogenation may as well be carried out in a continuous operation while using a high cylindrical vessel which is provided with several horizontal bottoms. The small rooms thus formed are connected with one another only by means of small holes in order to prevent a too fast mixture of the zinc dust suspensions in the various rooms of the reaction vessel. On the other hand, the zinc dust suspension in from 4 to 6 per cent aqueous caustic soda solution is allowed to flow continuously from the upper end to the lower end of the vessel.
Gaseous vinylacetylene is continuously blown into the zinc dust suspension at the-lower end of the vessel and is hydrogenated on its way to the upper end of the vessel. At the same time fresh zinc dust suspension is added continuously at the upper end substantially as fast as the spent zinc hydroxide suspension is removed at the lower end. The gases contained therein are set free and led back into the reaction vessel.
Example 4 2 liters of vinyl acetylene are shaken for several hours in a flask with a suspension of-.50 grams of zinc dust (85 per cent, obtained by electrolysis), 2 grams of copper powder, and 1 gram of butylnaphthalene sulphonic acid sodium salt in 200 cubic centimeters of 20 per cent caustic soda solution at 20 C. The vinylacetylene is thus hydrogenated practically completely to butadiene. The final gas contains only small amounts of hydrogen and only very small traces of butylene.
A similar result is obtained by shaking 2.5 liters of vinylacetylene with a suspension of 50 grams of zinc dust (85 per cent, obtained by electrolysis) and 2 grams of manganese powder in 200 cubic centimeters of 10 per cent caustic potash solution, or by reacting 2 liters of vinylacetylene under the same conditions with a suspension of 50 grams of zinc dust (85 per cent, obtained by electrolysis) and 2 grams of cobalt powder in 200 cubic centimeters of '5 per cent caustic soda solution.
Example 5 50 grams of phenylacetylene are shaken for several hours with a suspension of 100 grams of zinc dust, 10 grams of iron powder, 1 gram of butylnaphthalene sulphonic acid sodium salt in 200 cubic centimeters of 20 per cent caustic soda solution while excluding air. There is mainly obtained styrene (boiling point at 9 millimeters (mercury gauge) =33 C.) which may be isolated by known methods. The small amount of unconverted phenylacetylene may be separated by ammoniacal silver solution.
Example 6 2 liters of vinylacetylene are shaken for several hours in a flask with a mixture consisting of 50 grams of zinc dust (75 per cent, obtained by electrolysis), 3 grams of iron powder, 1 gram of butylnaphthalene sulphonic acid sodium salt, 81 grams of magnesium oxide and 400 cubic centimeters of water. The gas thus obtained mainly consists of butadiene. very little vinylacetylene, and only traces of butylene and hydrogen.
Example 7 butylene.
What we claim is:
1. A process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in aqueous solution of metal hydroxides dissolving in water with alkaline reaction with metallic zinc.
2. A process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueous solution of an alkali metal hydroxide with zinc dust.
3. A process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueous solution of an alkali metal hydroxide with zinc dust in the presence of a dispersing agent.
4. A process for the conversion of compounds ofrthe acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueoussolution of an alkali metal hydroxide with zinc dust in the presence of a metal capable of forming galvanic elements with zinc. I
5. A process for the conversion of vinylacetylene into butadiene which consists in treating vinylacetylene in an aqueous solution of an alkali metal hydroxide with zinc dust.
.6. In a continuous process for the conversion of. vinylacetylene into butadiene the step which comprises bringing vinylacetylene into close contact with an aqueous solution of an alkali metal hydroxide and with zinc dust, continuously removing the butadiene formed, and continuously adding alkali metal hydroxide solution and zinc dust substantially as fast as they are used up.
- WALTER REPPE.
ALEXANDER ROTHHAAS. OTTO SCHMIDT. ROLF LUEHDEMANN.
US193296A 1937-03-24 1938-03-01 Process of converting compounds of the acetylene series into compounds of the ethylene series Expired - Lifetime US2207070A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE2207070X 1937-03-24

Publications (1)

Publication Number Publication Date
US2207070A true US2207070A (en) 1940-07-09

Family

ID=7990075

Family Applications (1)

Application Number Title Priority Date Filing Date
US193296A Expired - Lifetime US2207070A (en) 1937-03-24 1938-03-01 Process of converting compounds of the acetylene series into compounds of the ethylene series

Country Status (1)

Country Link
US (1) US2207070A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2429411A (en) * 1947-10-21 I-alkoxy-z
US3450776A (en) * 1968-02-16 1969-06-17 Snam Progetti Process for the hydrogenation of water-miscible acetylene compounds into olefin compounds
US4115466A (en) * 1975-10-16 1978-09-19 Scm Corporation Synthesis of acetylenic compounds useful in preparing dehydrophytols and Vitamin E
US20140058146A1 (en) * 2012-08-21 2014-02-27 Uop Llc Production of butadiene from a methane conversion process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2429411A (en) * 1947-10-21 I-alkoxy-z
US3450776A (en) * 1968-02-16 1969-06-17 Snam Progetti Process for the hydrogenation of water-miscible acetylene compounds into olefin compounds
US4115466A (en) * 1975-10-16 1978-09-19 Scm Corporation Synthesis of acetylenic compounds useful in preparing dehydrophytols and Vitamin E
US20140058146A1 (en) * 2012-08-21 2014-02-27 Uop Llc Production of butadiene from a methane conversion process

Similar Documents

Publication Publication Date Title
US3128317A (en) Selective hydrogenation of acetylene in ethylene with a zeolitic catalyst
US3073865A (en) Process for catalytically reducing halogen-substituted aromatic nitro compounds to the corresponding amines
US2892801A (en) Catalysts
US2913505A (en) Process for separating olefinic hydrocarbons using silver fluoborate and silver fluosilicate solutions
KR930005254B1 (en) Method for producing cycloolefins
US2207070A (en) Process of converting compounds of the acetylene series into compounds of the ethylene series
US2207071A (en) Process of converting compounds of the acetylene series into compounds of the ethylene series
US1826974A (en) Process of producing hydrogen
US2019832A (en) Reactions of sodium with hydrocarbons
US2167203A (en) Process of manufacture of ketones and alcohols from olefins
US2954410A (en) Metalation process
US1895516A (en) Catalytic process of producing ketones
US1662421A (en) Production of primary amines
US2748108A (en) Processes of hydrogenation and to novel catalytic agent therefor
GB700397A (en) Improvements in or relating to processes for hydrogenation and to novel catalytic agents therefor
US2376252A (en) Oxide catalysts in dehydrogenation of cymene
CN110483242A (en) A kind of method of 1,4- butynediols hydrogenation synthesis 1,4- butanediol
US2500913A (en) Oxo synthesis followed by hydrogenation to alcohols
US2548728A (en) Preparation of nickel carbonyl
US3274272A (en) Process for the production of cyclohexene and methylcyclohexene
US1894763A (en) Purification of gases containing acetylene
US2377071A (en) Reduction of nitro compounds to amines by means of aliphatic hydrocarbons
US2300598A (en) Process of producing butene-2-diol-1, 4 and its substitution products
US1714636A (en) Production of formaldehyde sulphoxylates
US2249367A (en) Production of silver catalysts