DE1443768A1 - Hydrogenation process - Google Patents

Description

Patent attorney
DR.-ING. WALTER ABITZ

August 9, 1962

BiGELHARD INDUSTRIES INO. 113 Astor Street, Newark 2, N ₀ J ₀ , V.St.A.

Hyärierverfahren

The invention relates to the hydrogenolysis of Leichtkohlenwas seretoffen, in particular of non-cyclic, aliphatic light hydrocarbons with the production of methane- containing, gaseous reaction products.

The state of the art knows the use of base metal catalysts in the hydrogenolysis of Athan Hei etlachen

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Conditions * Tsar Craekurig of heavy hydrocarbons, such as gas oils _for the. at 232 ⁰ C and higher boiling l'eriperatur "cracking catalysts are known, which can also contain platinum. However, there is little knowledge about the use of noble metal catalysts in the hydrogenolysis of light hydrocarbons.

The present invention provides a new, advantageous process for the hydrogenolysis of non-cyclic, aliphatic, saturated and / or unsaturated light carbon, which has 2 to 7 carbon atoms in the molecule, with the production of methane. According to the more general method of operation according to the invention, a mixture of hydrogen and the light hydrocarbon with a metal of the platinum group as a catalyst, preferably on a (embossed, at elevated temperature, preferably from about 80 to 60O ⁰ O, to aaamraen) Contact at a temperature in the range mentioned, a hydrogenolysis of the light carbon / hydrogen molecules with the formation of methane "The process has the advantages that (1) the hydrogenolysis & θτ light carbons are effective and ■ ¥ @ 3? Liältiiisnäsalg!" follows, while dl © Öraekußg voiä IseieMkoklfSHwagges'stoffea "bisiiei ¹ r-Qlati ^ · s © lMie3? Ig % iar _f nmä 12) eis n © t! iaa} iiälisi | ps iiSOdisk'ögsi © asfliilt ^ äam © isa gateg Hateg H

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Ba & natural gas, which mainly consists of kethane, is often used for reasons of economy and expediency as Heisgae "and the burners for natural gas operation" are set to the correct intake of gas and air. One of the main problems of the protective gas industry has been " to develop processes which can be used as a substitute for the Brdgas in Spit ssen * The present invention is ideally suited for the production of methane when a low molecular charge is available.

It should also be noted that one of the main challenges in developing a substitute for natural gas is the reduction of unsaturated hydrocarbons, as the combustion of unsaturated hydrocarbons will result in yellowing of the flame tip and deposition of ruse. The reduction of the ungesfittigten hydrocarbons to methane has proved difficult, d _o h. could only be carried out at high temperatures with resulting strong carbon formation. The present invention enables the reaction of the unsaturated hydrocarbons with Hp to form CH. at relatively low temperatures O

The achievement of relatively easy hydrogenolysis of light hydrocarbons with the invention is unexpected

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and surprising, since the cracking of such spawning hydrocarbons has hitherto been of a lower molecular nature than cracking Hydrocarbons, which contain more than 7 carbon atoms in the molecule, was difficult »Sine easy hydrogenolysis ▼ on hydrocarbons with 2 to 4 carbon atoms in the molecule geuäss the invention is particularly important land has been considered worthwhile »

The Me tulle the metal group erflndungsgemUss be used as catalysts are preferably located on a Trliger, z, for example activated alumina ₉ carbon Sllioagel, diatomaceous earth and Konblnationen same · Bas platinum group metal is preferably rhodium, ruthenium, palladium, platinum. or a combination thereof, b. B. of ruthenium and platinum, ruthenium and palladium and rhodium and platinum. Preferably the amount of catalyst metal is about 0.1 to 5; e in particular about 0.3 to 2 wt. #, because of the catalyst metal and support. The degree of oxygenation changes with the particular catalyst used. frager and the K & taIyeatorkonsupretetion.

Piir the Zweoke of the invention, temperature · »of about 80 to 600 ⁰ C are bevoreugt as temperatures well above 6Ö0 ° C au Heigung a greater Kokebildung yield. Temperatures that are far below & 0? P should be avoided because at

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no significant hydrogenolysis is obtained from such teuperatyrene. The optimum temperature depends on the nature and concentration of the catalyst as well as the nature and concentration of the reactants. Particularly preventive catfish are used for hydrogenolysis of ethane-containing gas when working with a rhodium catalyst, temperatures between 200 and 300 ° C, with a ruthenium catalyst between 125 and 40O ⁰ C, with a palladium catalyst between 300 and 400 ° 0, a ruthenium-platinum Catalyst between 210 and 30O ⁰ C and with a ruthenium-palladium catalyst between 220 and 450 ⁰ C applied.

The hydrocarbons treated according to the invention are nioht oyolieche, aliphatic © light hydrocarbons that saturated and / or unsaturated and substituted and / or unsubstituted. The number of carbon atoms in the. Hydrocarbon molecules can range from 2 to 7. Examples of such hydrocarbons are ethane, ethylene, Propane, propylene, butane, butene-1, hexane, n-IIexylene, pentane, Pentene-1, heptane, heptylene and 2,2-dimethylbutane.

The output level may contain hydrogen in various proportions, and the degree of hydrogenolysis depends on the Proportion of hydrocarbons to hydrogen in the carbon dioxide gas. the stoohionetric sur reaction with the entire carbon

• ■ 5, -. _ ORIGINAL BATHROOM

0Ö9813 / 127 2

Hydrogen with the formation of methane necessary {! Close equivalent. Hydrogenolysis reactions benefit from the invention Use of ethane (1) or pentane (2) as a hydrocarbon and:

(1) C ₂ H ₆ + H

(2) C ₅ H ₁₂ +

Be is desirable »if possible, relatively pure sound tones as To use reaction parts, as this normally does the life of the catalyst is extended by burning off the carbon and bsjv /. or sulfur Regenerate treatment with an oxygen-containing gas.

The rough speeds can be up to 20,000 tree parts (Horzaal conditions) Gas / rough part of catalyst / hour is enough, A room temperature of about 1000 to 10000 parts by volume of gas (normal conditions) / part by volume of catalyst / hour is preferred · The reaction can be carried out at pressures ranging from about 0 to 70 attt.

The following examples serve to further explain the Invention·

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Belapiel 1

With metering by means of a Hotatlonsdurohflußmessere (Rotaneter) a mixture of 55 mol # ethane and 45 M0I36 hydrogen is introduced into a reaction device of 2 1/2 on Durohmesser, the 20 ml catalyst in the form of 0.5 pounds of Ru to 3.2 raa pellets containing from activated alumina (Al ₂ O ^) from a temperature of about 22O ⁰ C. The gaseous products obtained are analyzed by means of an ultra-red spectrophotometer, which results in a methane content of 85 Hol £.

Similarly, other mixtures of hydrocarbon and hydrogen gas according to Table I on the hydrogenolysis investigated on the ruthenium catalyst · The results are called the table I.

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Table I. Eatal ytischa! Fc ^

fdo XohlgRwaaeergtoffen

Catalyst

Pressure

ϊιϊΙ O _t 5 £ Hu on 5ί2-22π-Ρβ11βΐβ from activated aluminum oxide

Xtauffigeaehwla- 2000 ItIs 3000 Reirateile (horBal conditions) / dlgkelts Hauiitell Katulyaator / hour

Coal- T «apera-added good, Afeatg» M »ndeg good.

Waeeer door of the MoHC «ιτ« Μ · η «

Sohjoht, _H Coal- CH. ² waeeer

^cd waeeer- * fabric +)

waeeer-

Ethane

147 249 297

95

It

5.0 <0 _f 02 95

ti It

90

0/6

0.2

4> 5

11

Propane 159 97 3.5 <O, O2 90 low 3.5

■ Quantity - · ■

246 «« '«84 - 16

- '»not analyzed +) A see first column

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Vert «of Table I show that a ruthenium catalyst in the presence of hydrogen the cracking of aliphatic, , saturated light coal waeaeratoifen with the formation of methane calls for

When I came up with Table I, I found it easier Consideration of minor components of the "! Led tone". drowning oaee omitted. Apparent biscuits In the yield and the analysis of the Geaautproduktgaee lie within the previous and analysis limits of the methods used.

According to the work experience, example 1, gaegenieohe with internal biiiweneetung in the range of 5 mol% ethane and 95 ma * wceaeretoff up to 99% (ethane, 0.15 mol methane, 0.85 % WaiSjst Jlthjrlett and no waeeeretoff under

Au «b« ut «M Jlithan elngeetst with veraohieden tenper doors.

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ga T> e 1 X _M e; , 11

flea catal ysators a ui iithaa ^ Wa aagyatof t - g amiscSie catalyst * $> Eu on 5 "2" i8a-Pellet0 aua activated bridge: 0 atü

Rauugeschivin- 2000 to 3000 Hairat © il © {Homalöediiijungen digkeit «til Ktlat / StU ^

Temperature flor gehiclit,

3 part Katalyeator / StcU good ■ ***) »AbatrgHanfi ea

MoIg

O ₂ H ₆

CH _a Mon 1 #

OH,

door C »r« reohpat) for «ine CH.-Auebeütt

YOB JOO *,

147 202 249 297 329

150 202 253 • 400

217 295 355

127 154 194 326

246 383.

95

IS

ti

Il II.

86

ti

Jl ti

55

M Il

18th

0.

5.0

Il

Il

14 η

H Il

45

"1

82 η

99

H -

<0 _f 02

• η

η it

■ '0.03

.51 'Ίί -

η it

0 _f 15

η ■ 90

72
72

10

.2.0
<0 »Ό2

ias sngsfttHrtft Genisch

the aljstranende Gemioch 0 _r

co |, 1.6 iioi ^

+++) as an impurity

- «not analyzed.

1.0 <02

6.0 :
C0.002

«0.02
<0, Ö2

86 64

67

m a »·

4.3

11 12

28 28

85 86

88

40 35

0.14 0.12 0 | 30 + *>

0.72

330

250

220

150

.at

before,

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Dl · values of table ZI beige that in hydrogenolysis τοπ Ithaa with constant catalyst and other conditions the degree of hydrogenolysis sloh alt the temperature and the Xonsentrationen dee λthane and hydrogen in the supplied Genlsoh changes.

Table II further shows that the Ru catalyst, in the presence of H ₂ ^d1 · Oraokung, produces a starting mixture of 82 hol * ithan and te mol * of hydrogen and the axial yield is one Tenperatur τοη approximates 150 ⁰ O, while in the absence of clay hydrogen up to 383 ⁰ O no dangerous oraokung ia Xthane occurs (99 *)

Example 3

According to the working method in Example 1, an Oeaieor ^ on 41 Itelift C ₂ H ₆ and 49 MoI ^ hydrogen in a heating unit, the 10 «1 catalyst in fona τοη '0.5 Jt Bu to 3.2HBm-PeIIete on the activated Al Contains ₂ O _3. In a similar manner, mixtures of approximately the same gas / air mixture are put into other heaters using other catalysts (Table XII).

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Effect of 1 catalysts 174 : 450 . ., · Renas] on the promotion of valid > n) / yeah part Hydrogenolysis of ethane 17th aut, ι, Mol? * to C ₂ H ₆ Catalyst & ge ι JO mk _; ... . 197 370 10 St. 9 A. I. 27 ■ RaoegesehiBissdl. ^ Tei'fes 4000 ilausifc ^ ilas :( , 238 ■ 425 / · ZVLfi & i > · HoIi t ++) 0 47 0.05 VJl 5.0 Pressure: 0, sfJ, '' '"-'. + t) * Bae »ugled Geniedh contains 0 CO
ι!> ■ JT mn II'11 OH ₄ ££ ♦. ÜÄ 79 <0.02 <0.002 Catalyst 'f 210 - · not analyzed « 0.48 boasted 14th 1.5 41 0.6 86 <P, O2 : 3 ^ 0 N H ₂ η it η Catalyst / hour 20th <0.002 O ₉ 5 ft Eu avf - ^ ₉ § «! Ia3» Pel, let8 ' ■; 400 . M. 49 η η η 30th 32 * from activated Ll ₂ OZ 420 ti 44 ■ '40 - #, 02 38 jM '. . ■ ■,. , ■. · 0.36 dd 14th 1.7 * ¹ Outflowing 36 28: <0.02 44 ^ 0.5? T Hh on 2.2 ME Pe lie ta 0.36 14th 1.6 41 CO 19th <0.02 34 t from activated Al ₂ O * * * • -210 N 49 η η η 40.06 6.6 30th <0.02 I.
· * 0.5 5t? I on 3 »2-SBB-Pellitö; f ^! η 49 It It <0.06 10 PO aue activated AIgO- ■ Λ "^>/;"'" 240 0.36 η 14th 1,, 6 41 <0.06 6.0 ■ ^: 1 & ^; i0 02 ί 490 η 48 11 i 5t pt on Kdhlenetoft 370 0.36- 49 14th 1 # 7 41 0.0060 8th • "τ5 <0, G2 45 0.3 1 »'pt * 0.2.3t Hu on s 5 9t Co on 3.2-zani-Kugeleben 280-350 <0.0005 45; , 15 0 ^ 69 4 * O-ap »pellets from acti ^ t: - from AIgO * ^ jV, ";.. · ;.>'.. ^{,, ..-.;} ' r · ■; · ■
Hbpcallte (Ag-Ma) - i 0.40 49 14th 1.6 41 <0.0005 48 75 0 42 ^ fourth », AIgO *: 'V >> * - ^: " η η W. It ^ 0.0005 48 P, 03 42 - ^ 0.4 5t Pd .4 0.1 # Eu on ' finely divided a copper . "' 49 . η • "·. tr. 0.34 47 % • ^ - ^ '· 43 co 4.0 mm pellets from activ '·. - ■ · ■ .. 0.36 H 1.6 41 47 14th bl40 «SJ tem Al ₉ O- '■: · ■■ · ■ -''■' * · ■■■ - ■ ·. ■■ ■■; » 4.36 η 14 ' ^;: 42 "" · <0, C060 14th ^ 0.02 43 · co CD ■■ ^M. 49 'η "It η 14th <0.02 O
Ξ2 0.36 49 14- 1.6 42 <0.0005 M. η . * · 0.50 • > .07 mi 49 • ■ ■ * ■ '. 0.26 0.34 0.36 0.28 0 _t 24 -

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Me results from Table III show that the ease the ethane hydrogenolye β loh with the catalyst alleviates. Bs It can also be seen that ruthenium and rhodium are particularly effective in promoting this reaction at relatively low temperatures, and that ruthenium in combination with platinum and ruthenium in combination with palladium-effective catalysts results.

Example 4

laoh the working method of example 1 over 10 ml of Pd-Katalyeator Oenieche of iithane and hydrogen are passed, whereby Catalysts of various types can be used (Table IT). .

■■; .. / _v '. . bath

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O ca ο

43

QJ &

• β

SVi cm cvi ενι sy

© po QO

ooo

OOO

ö so Ο "*

OO- *

4 »

O Ό

ϋίΜΛΙΑ α \

OOO "· O ·

OOO 6 *>! Ä> .OO

OOO; «- 8A Otn

OOO OO OO

■ «! • ε s

"-"it

SS

O O

ν ->

VO

SVi O

Os ε O3 OS fc

OOO V9 C) ^

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The fourth of Table IY show that the ease of Hydrogenolysis with the metal content of the catalyst Bun increases »

The general findings in Example 1 on the obtained Experiments also apply to Tables II, III and IV.

Example ?

The following experiments explain the requirement of the hydrogenolysis of an unsaturated and a branched-chain, aliphatic alcoholic waeeeretoffe with the formation of methane by means of a metal of the platinum group as a catalyst in the presence of hydrogen · The experiments are carried out at 0 atm carried out.

According to the procedure of Example 1, about 41 mols of O ₂ H ₆ , 14 mols of OH ₄ , 1.5 mols of C ₂ H ₄ , 0.48 of Hol * CO, 0.07 of Hol * O ₂ , remainder of H _{2 are passed} through a ratemeter measured into a reaction device containing 10 ml of catalyst in the form of 0.5 $> Ru

. 3.2-mn-Pelleta from activated Al ₂ O ^ contains, it is about 4000 Raua parts (normal temperature) / Raua part of catalyst / hour at 174 ⁰ C 0.03 mol * non-unset ethylene and at 197 ⁰ O non-unset ethylene in amounts <0.02 mol *, with considerable amounts of

attack.

8098 1 3/1 272 -15- bad original

To transfer a mixture of hechexane (99 mol ^) and hydrogen over the catalyst, hydrogen is bubbled through neohexane in fine bubbles, using a neohexane-filled "microbubbler" * and over 20 al catalyst in Fona from Ru to 3 »- ram -Pellets made of activated Al ₂ O *, the space velocity is 4750 parts by volume (normal conditions / space part catalyst / hour Bas inflowing mixture contains 45 »5 HoI ^ neohexane and 54 * 5 Hgo cold trap connected in Heihe isto the analysis of the effluent gases shows daae at 9O ⁰ C 4 »O Mo1 $ CH ₄ and higher Eenperaturen considerable amounts of CKL form" the Ultrarotanalyse the effluent mixtures shows at temperatures up to 432 ⁰ C, no formation of other Reaction products as OH40

Bin® exact Mengenbestiianung has not been performed, dig h® ± Temperatures below 200 ⁰ C obtained »methane

were i © r invention further execution eSornen,

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Claims (1)

Claims 1. Process aur hydrogenolysis of non-cyclic, aliphatic boron hydrocarbons, thus rewarded, daaa nan a mixture of hydrogen and the non-cyclic, aliphatic borrowed hydrocarbon, the 2 to 7 Carbon atoms in the molecule contains »with a metal of the Platinum group eusmebringt ale catalyst at elevated temperature and thereby the hydrogenolysis of the hydrocarbons with the formation of methane-containing gaseous Reaction products causes. 2 »Process aur hydrogenolysis of non-cyclic, ali Phatieohen light hydrocarbons, characterized by the fact that you get an oenia of hydrogen and the non-cyclic, aliphatic light carbon, which contains 2 to 7 carbon atoms in the molecule, with a metal of the platinum group on a support as a catalyst at a temperature in the range of about 80 bia 600 ⁰ G euouiinenbrngt and thereby causes the hydrogenolyels of the hydrocarbon with the formation of methane-containing gaseous reaction products. 3 · Method according to Anopruch 2, thereby gekenßaei ^ hnet ^ daee as non- cyclic, aliphatic Leiointkohlonwaefierfitoff Χ than one is. "17" BAD ORIGINAL ο method according to claim 3, characterized in that rhodium is used as the metal of the platinum group and works at a temperature between 200 and 30O ⁰ C. 5 × The method according to claim 3, characterized gekennsselehnet that nan ala platinum group metal used ruthenium and operates at a Tenperatur between 125 and 45O ⁰ C. 6. The method according to claim 3, characterized in that one as metal ,! the platinum group uses palladium and works at a temperature between 300 and 400 ⁰ C 7 · seduction according to claim 3, characterized in that men as a platinum group metal ruthenium and platinum is used and operates at a Tenperatur 210-300 ⁰ C. Method according to Claim 3, characterized in that the metal of the platinum group is ruthenium and palladium veiinrendet «ad at a deuperature between 220 and 450 ° E is working. ¥ learned? @ 2i from? Hydrogenolysis van noncyclic, all- ^ eichtkohlenwasse ^ materials »thereby gekenisssielv rasa eis C «iis © li by W © ssoretoff and the ^r '^; ll ä PlM f I tl as ICß ^ a BATH iO9813 / 12? 2 .41 at elevated temperature and thereby the Hydrogenolysis of the hydrocarbons causes the formation of τοη methane-containing gaeförnigen reaction products. 10. The method according to claim 9 _f, characterized in that one works at a temperature of about 80 to 600 ⁰ C « BAD - 19 809813/1272